BINDURA UNIVERSITY OF SCIENCE EDUCATION

CH 302

Organometallic
Chemistry

Lecture Notes
Norman Mudavanhu

E-Mail:
[email protected]
 Sabhuku Mudavanhu
Intro 2

CH302 - Organometallic Chemistry

Norman Mudavanhu (office: B12, phone: 0772652143) E-Mail:
[email protected]

This is an advanced undergraduate, introductory graduate level course that covers the organometallic
chemistry of the transition metals with emphasis on basic reaction types and the natural extensions to the
very relevant area of homogeneous (and heterogeneous) catalysis. A course outline is shown below:
A. Ligand Systems and Electron Counting
1. Oxidation States, d electron configurations, 18-electron "rule"
2. Carbonyls, Phosphines & Hydrides
3.  bound carbon ligands: alkyls, aryls
4. /-bonded carbon ligands: carbenes, carbynes
5. -bonded carbon ligands: allyl, cyclobutadiene, arenes, cyclopentadienyl
6. Metal-Metal bonding
B. Fundamental Reactions
1. Ligand substitutions
2. Oxidative addition/Reductive elimination
3. Intramolecular insertions/eliminations
C. Catalytic Processes
1. Hydrogenation: symmetric and asymmetric
2. Carbonylations: hydroformylation and the Monsanto Acetic Acid Process
3. Polymerization/oligomerization/cyclizations

Recommended Text: "The Organometallic Chemistry of the Transition Metals" by Robert Crabtree (4th
Edition, Wiley). Reference Text: “The Principles and Applications of Transition Metal Chemistry”, by
Collman, Hegedus, Norton and Finke (1st or 2nd eds, University Science Books).

Study The class will form study groups of 1-6 students to work together on the homework
Groups: (each student hands in their own copy of the HW) and to answer questions in class
(work alone on quizzes & exams).
 Sabhuku Mudavanhu
Intro 4

Fundamentals You Need to Know:

1. Electronegative/Electropositive concepts
Where do the partial positive and negative charges in a
molecule reside? This is important for determining how
much electron (e-) density will be donated from a ligand to
a metal and where a nucleophile or electrophile will likely
attack for chemical reactions.

2. Lewis dot structures and valence electron counts

Important for determining the number of electrons on a
ligand and what the charge of the ligand is. We almost
always deal with ligands with even #’s of electrons. If a
ligand has an odd # of electrons we add additional
electrons to get to an even #, usually to form a closed shell
electron configuration with a formal negative charge(s).
Exception = Boron.

3. Oxidation States
4. Organic line notation for drawing structures
Cl Cl Cl Cl
Cl Cl

Cl Cl Cl Cl
Cl Cl Cl Cl
Ni Ni
R2P PR2 Cl
R2P PR2 Cl
Ni
R2P PR2
 Sabhuku Mudavanhu
Intro 5

Electron Density Terminology 101:

Electron Density: The presence of higher energy valence electrons
around an atom. Electrons are represented by a probability distribution
spread out over a region of space defined by the nature of the orbital it
resides: s, p, d, f, and/or hybrid orbitals such sp3, sp2, sp, etc.
Atoms with quite a few valence electrons such as Pt(0) d10 and/or
contracted orbitals have a high electron density. Atoms with fewer
valence electrons (e.g., Na+) and/or diffuse orbitals (electrons spread out
over a larger region of space) can be considered to have low electron
densities. Do not confuse electron density with electronegativity.
Electron-rich: Atoms that are willing to readily donate electron pairs
to other atoms are called electron rich. Ease of ionization is another
property associated with electron-rich atoms. The willingness to share
or donate electron pairs is related to lower electronegativity, larger
numbers of valence electrons, good donor groups on the atom in
question, negative charges, or some combination of these factors. Using
organic terminology I would consider an electron-rich atom to be a good
nucleophile (electron pair donating).
Electron-deficient (poor): Atoms that are NOT willing to donate or
share electron pairs to other atoms are called electron deficient (poor).
These atoms typically have lower lying empty orbitals that can accept
electron pairs from other atoms. The un-willingness to donate or share
electron pairs could be caused by high electronegativity, cationic
charge(s), lack of electron pairs, or some combination of these. I would
consider many (but not all) electron-deficient atoms/molecules to be
good electrophiles (electron-pair accepting) and certainly poor donors.

Examples:
Fluoride anion, F: This anion has high electron density due to the
negative charge, filled octet of electrons, and small size. BUT I would
NOT consider it to be electron-rich, meaning a good electron donor.
The extremely high electronegativity of a fluorine atom means that it
 Sabhuku Mudavanhu
Intro 6

desperately wants to pick up an extra electron to form the fluoride

anion, which is extremely stable. The filled valence orbitals are fairly
low in energy for F and generally poor donors. It is certainly not
electron-deficient as it doesn’t have any low-lying empty orbitals and
does not want to accept any more electrons. It isn’t electron-rich either
since it is a very poor nucleophile and generally a poor ligand for most
metals (except those in high oxidation states). It is almost impossible to
chemically oxidize F.
Methyl anion, CH3: This anion is very electron-rich and a powerful
nucleophile. The electron-richness comes from the lower electro-
negativity of carbon and the high energy of the anionic sp3-hybidized
lone pair that makes it a strong donor group. It is also very easily
oxidized, pointing to the presence of a high-energy lone pair orbital.
PMe3 vs. P(OMe)3: The methyl groups are considered to be electron
donating making the P center more electron-rich. The methoxy groups
are  electron-withdrawing due to the electronegative oxygen atoms,
making the P center more electron deficient. The results from Density
Functional Theory (DFT) calculations on both are shown below. Note
the higher energy of the P lone pair (highest occupied molecular orbital,
HOMO), greater spatial extent (generally better overlap with metal d-
orbitals), and lower positive charge on P for PMe3 relative to P(OMe)3.

PMe3
HOMO = 5.03 eV
Charge on P = +0.22

P(OMe)3
HOMO = 7.40 eV
Charge on P = +0.75

MO plot of the lone pair orbital (HOMO) for PMe3. Dashed outline
indicates the spatial extent of the lone pair for P(OMe)3.
 1 18
1
Periodic Table of the Elements 2
H 2 13 14 15 16 17 He
Hydrogen Helium

3 4 5 6 7 8 9 10
Li Be B C N O F Ne
Lithium Berylium Group 8 Boron Carbon Nitrogen Oxygen Fluorine Neon

11 12 13 14 15 16 17 18
Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar
Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine Argon

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ge As Se Kr
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Galium Germanium Arsenic Selenium Bromine Krypton

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon

55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon

87 88 89 104 105
Sabhuku Mudavanhu

Ra Ac
Francium Radium Actinium

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium

90 91 92 93 94 95 96 97 98 99 100 101 102 103

Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
Intro 7
 Sabhuku Mudavanhu
Intro 8

General Trends for the Transition Metals

Early Transition Metals Late Transition Metals

low electronegativities higher electronegativities

higher oxidation states lower oxidation states

“harder” metal centers “softer” metal centers

OXOPHILLIC!!
 Sabhuku Mudavanhu
Intro 9

Transition Metal Catalysis

[catalyst]
A + B C
A catalyst is a substance that increases the rate of rxn without itself
being consumed (but it is involved!) in the reaction. After the rxn is
finished you should be able to recover the catalyst from the rxn
mixture unchanged. A catalyst speeds up the rate at which a
chemical reaction reaches equilibrium. The overall
thermodynamics of the rxn is NOT changed by the catalyst.
Therefore, very endothermic (non-spontaneous) reactions are
usually NOT suitable for catalytic applications.
A catalyst provides a lower energy pathway for the production of
products from reactants, thus allowing the rxn to proceed faster. It
lowers the activation energy for a rxn (kinetics) – it does NOT
change the thermodynamics of a rxn.

Catalyzed rxn
proceeding through
an intermediate

Ea

Ea
G catalyzed

Reactants
G

Products

Reaction Coordinate
 Sabhuku Mudavanhu
Intro 10

A catalyst provides an alternate mechanism (or pathway) for the

reactants to be transformed into products. The catalyzed
mechanism has an activation energy that is lower than the original
uncatalyzed rxn. An excellent catalyst will lower the activation
energy the most.

An example of a Pt-catalyzed reaction is shown below:

Pt(ethylene)3
+ HSiMe3 SiMe3

Hydrosilylation

Me
Me
1. oxidative addition
ligand addition Pt 2. ligand dissociation

+ propene + HSiMe3
Me
- alkene

Pt SiMe3
Pt
H

SiMe3 + propene
Pt

SiMe3 1. migratory insertion

2. ligand addition

reductive elimination

Note that there are different numbers of ligands (a generic name for
anything that bonds to a metal center) on the metal. Too many is
bad, too few is bad. How can you tell how many to use?? Electron
counting is the key, which is presented later in this chapter.
 Sabhuku Mudavanhu
Intro 11

Some Important Ligand Nomenclature

Chelate Effect “chelate” is from the Greek meaning “claw” or
to grab on to. The chelate effect or chelation is one of the most
important ligand effects in transition metal coordination chemistry.
Since most metal-ligand bonds are relatively weak compared to C-C
bonds, M-L bonds can often be broken rather easily, leading to
dissociation of the ligand from the metal. Consider the two metal ligand
complexes shown below:
L L

M L M + L

L L
L
M L M
The second metal complex is much less likely to lose one of the
ligands due to the bridging group that holds the ligands in proximity to
the metal center. From a kinetic viewpoint, if one of the ligands
dissociates, it will remain close enough to the metal center to have a
high probability of re-coordinating before another ligand can get in an
bind. From a thermodynamic viewpoint, by tethering two donor ligands
together, one removes the entropic driving force for dissociating a
ligand and thus making more particles in solution (more disorder).
The chelate effect can be extremely dramatic. There are cases known
where the presence of a chelate will change the equilibrium constant by
a factor of 1010 favoring the coordinated form of the ligand to the metal
over the dissociated form. Naturally, the longer and more flexible the
bridging group in a chelating ligand, the less dramatic the chelating
effect. It is possible to design ligands with sterically enforced chelates.
 Sabhuku Mudavanhu
Intro 12

x “eta-x” was originally developed to indicate how many

carbons of a -system were coordinated to a metal center.
Hapticity is another word used to describe the bonding mode of a
ligand to a metal center. You will occasionally see hx used instead of
x, although this usually an error caused by forgetting to turn a regular
font h into the symbol font on most word processors in order to get a
Greek . An 5-cyclopentadienyl ligand, for example, has all five
carbons of the ring bonding to the transition metal center.
x values for carbon ligands where the x value is odd usually
indicate anionic carbon ligands (e.g., 5-Cp, 1-CH3, 1-allyl or 3-
allyl, 1-CH=CH2). The # of electrons donated (ionic method of
electron counting) by the ligand is usually equal to x + 1. Even x
values usually indicate neutral carbon -system ligands (e.g., 6-
C6H6, 2-CH2=CH2, 4-butadiene, 4-cyclooctadiene). The # of
electrons donated by the ligand in the even (neutral) case is usually
just equal to x.

M
M
M M M
5-Cp 3-Cp 3-allyl 1-allyl

The nomenclature, however, has been generalized by some in the

organometallic field to include non-carbon ligands when there is some
question as to the bonding mode (or hapticity) of the ligand donor atoms
to the metal. For example, the bisphosphine Ph2PCH2CH2PPh2 (dppe)
is normally a chelating ligand, but there are metal complexes known
where only one of the phosphine atoms is coordinated to the metal
center and the other is “dangling.”
 Sabhuku Mudavanhu
Intro 13

The nomenclature for such a singly coordinated bisphosphine ligand

would be: M(1-dppe) -- meaning that only one of
the two possible phosphorus atoms is bonded to
the metal. Note that in cases like this, having an M PPh2 PPh2
odd hapticity does NOT mean that the ligand is 1-dppe or 1-dppe
anionic (it is, however, a 2 electron donor!). When
dppe is coordinated in its normal chelating mode, one usually omits the
2-designation, as this is considered redundant. Note that many authors
(especially non-Americans) use x instead of x when referring to non-
carbon ligands. I will generally use the kappa notation.

x “mu-x” is the nomenclature used to indicate the presence of a

bridging ligand between two or more metal centers. The x
refers to the number of metal centers being bridged by the ligand.
Usually most authors omit x = 2 and just use  to indicate that the ligand
is bridging the simplest case of two metals.

Problem: Which of the following ligands will chelate

the strongest to a generic metal center? Why?
A) B)

Me2P PMe2
Me2P PMe2

C) D)

Me2P PMe2 Me2P PMe2

 Sabhuku Mudavanhu
Intro 14

Ordering There is no set method of naming or ordering the listing

of metal and ligands in a metal/ligand complex that most authors follow.
There are IUPAC formalisms, but hardly any inorganic/organometallic
chemists follow them.
There are some qualitative rules that most authors seem to use in
American Chemical Society (ACS) publications:
1) in formulas with Cp (cyclopentadienyl) ligands, the Cp usually
comes first, followed by the metal center: Cp2TiCl2
2) other anionic multi-electron donating ligands are also often listed in
front of the metal, e.g., trispyrazolylborate anion (Tp)
3) in formulas with hydride ligands, the hydride is sometimes listed
first. Rules # 1 & 2, however, take precedence over this rule:
HRh(CO)(PPh3)2 and Cp2TiH2
4) bridging ligands are usually placed next to the metals in question,
then followed by the other ligands (note that rules 1 & 2 take
precedence): Co2(-CO)2(CO)6 , Rh2(-Cl)2(CO)4 , Cp2Fe2(-
CO)2(CO)2
5) anionic ligands are often listed before neutral ligands:
RhCl(PPh3)3, CpRuCl(=CHCO2Et)(PPh3) (neutral carbene ligand),
PtIMe2(C≡CR)(bipy).
 Sabhuku Mudavanhu
Intro 15

Common Coordination Geometries

6-Coordinate: Octahedral (90° & 180° angles)

L L
L L L
M L M L M
L L L L
L
L L L
5-Coordinate: Trigonal Bypyramidal or Square Pyramidial
(90° & 120°) (~100° & 90°)
L axial L apical

L L L
L M equitorial M
L L L basal
L
4-Coordinate: Square Planar or Tetrahedral
(90° & 180°) (109°)

L L

L M L M
L
L
L L
Square planar geometry is generally limited to Rh, Ir, Ni, Pd,
Pt, and Au in the d 8 electronic state when coordinated to 2e-
donor ligands.
 Sabhuku Mudavanhu
Intro 16

Problem: Sketch structures for the following:

a) CpRuCl(=CHCO2Et)(PPh3)

b) Co2(-CO)2(CO)6 (Co-Co bond, several possible structures)

c) trans-HRh(CO)(PPh3)2 [Rh(+1) = d8]

d) Ir2(-Cl)2(CO)4 [Ir(+1) = d8]

e) Cp2TiCl2
 Sabhuku Mudavanhu
Intro 17

Bonding and Orbitals

z
s
x
y

z z z

x x x
y y y

pz px py

z z

x x
y y

d z2 d x 2 - y2
z z z

x x x
y y y

d yz d xz d xy
 Sabhuku Mudavanhu
Intro 18

Orbital Overlap Efficiency

The strength of a chemical bond (covalent or dative) is related to
the amount of overlap between two atomic (or hybrid) orbitals.
When dealing with -bonds the overlap efficiency is important.
This is illustrated below for the -systems of ethylene
(H2C=CH2) and silylene (H2Si=SiH2). The Si=Si double bond is
very weak and reactive because the amount of overlap (green
areas) between the two p-orbitals is small relative to the parts
that do not overlap. The overlap efficiency can be thought of as
the orbital overlap area divided by the non-overlapping area.
The smaller this ratio, the weaker the bonding.

For -bonds the overlap efficiency is close to 1.0 (100%

overlap), which nicely explains why -bonds are usually
stronger than -bonds.
 Sabhuku Mudavanhu
Intro 19

Overlap efficiency also applies to -bonds between atoms. Bond

strengths can vary as the bond overlap spreads out over a larger region
of space. This is not simple to qualitatively predict. For example, the
dihalogen bond strengths increase F2 < Cl2 < Br2 < I2. But decrease as
one goes from C-C > Si-C > Ge-C > Sn-C > Pb-C. For most transition
metal M-M single bonds the trend is fairly consistent: first row <
second row < third row. But for M-M quadruple bonds one has: Cr-Cr
<< Mo-Mo > W-W.
In the case of strong multiple bonding and shorter bond distances one
can get TOO much overlap between -bonding orbitals. This can lead
to destabilizing anti-bonding type interactions that weaken the -bond.
N2 is a good example of this:

The p- orbital is higher in energy (& the HOMO) than the -bonding
orbitals. Bringing two p- orbitals together to the N≡N bond distance
leads to anti-bonding interactions due to the p-lobe extending over into
the other phased orbital region as shown qualitatively below:

To minimize this unfavorable antibonding interaction N2 forms a sp

hybrid orbital combination that reduces the -bonding overlap in favor
of the two stronger (overall) -bonds.
 Sabhuku Mudavanhu
Intro 20

Square Planar
Square planar complexes typically have d8 (sometimes d9)
electronic configurations and are usually limited to the following
elements: Rh, Ir, Ni, Pd, Pt, Cu, & Au.
Of these the first and second-row metals add a fifth ligand more
readily than the third-row analogs. The reason that Ir, Pt, and Au
are less likely to add a fifth ligand is due to the blocking effect of
the filled 5dz2 orbital that is more spatially extended than the 3 or
4dz2 orbitals. The 6pz orbital is also more contracted than one
would expect due to relativistic effects that allow better
penetration of the s and p orbitals to the highly charged nucleus
lowering their energy. The d and f orbitals are shielded better
that raises their energies. This effect really turns on for Pt and
Au, less so for Ir that does have more of a tendency to pick up a
fifth ligand.
The relative orbital extents of the filled dz2 and empty pz orbitals
from DFT calculations on MH2(NH3)2 model complexes for Ni,
Pd, and Pt are shown below.
 Sabhuku Mudavanhu
Intro 21

Octahedral Orbital Diagram

 Sabhuku Mudavanhu
Intro 22

18 Electron "Rule"
Organic compounds, of course, follow the 8 electron rule: there can
only be a maximum of 8 valence electrons around a carbon center.

The vast majority of stable diamagnetic organometallic compounds

have 16 or 18 valence electrons due to the presence of the five d
orbitals which can hold 10 more electrons relative to C, O, N, etc.

Electron counting is the process of determining the number of

valence electrons about a metal center in a given transition metal
complex.

To determine the electron count for a metal complex:

1) Determine the oxidation state of the transition metal center(s)
and the metal centers resulting d-electron count. To do this one
must:
a) note any overall charge on the metal complex
b) know the charges of the ligands bound to the metal
center (ionic ligand method)
c) know the number of electrons being donated to the metal
center from each ligand (ionic ligand method)
2) Add up the electron counts for the metal center and ligands
Complexes with 18 e- counts are referred to as saturated, because
there are no empty low-lying orbitals to which another incoming
ligand can coordinate. Complexes with counts lower than 18e- are
called unsaturated and can electronically bind additional ligands.
 Sabhuku Mudavanhu
Intro 23

Exceptions to the 18e “Rule”

Early Transition Middle Transition Late Transition

Metals Metals Metals
16e- and sub-16e- 18e- configurations 16e- and sub-16e-
configurations are are common configurations are
common common
Coordination Coordination Coordination
geometries higher geometries of 6 are geometries of 5 and
than 6 relatively common lower are common:
common d8 = square planar

d6
 Sabhuku Mudavanhu
Intro 24
Ligands, Bonding Types, Charges, and Electron Donor Numbers

Ligand Name Bonding Type Formal Electrons

Charge Donated

Molecular Hydrogen: H2 H 0 2
M
H
Hydride: H M-H -1 2
Hydride: H H -1 2
M M
Halide: X M-X -1 2

Halide: X X -1 4
 bridging (2 to
M M each M)
Halide: X X -1 6
3 bridging (2 to
M M each M)
M
Alkoxide, thiolate: OR, SR M- OR -1 2 or 4

Alkoxide, thiolate: OR, SR R -1 4

 bridging (2 to
O
each M)
M M
Alkoxide, thiolate: OR, SR R -1 6
3 bridging O (2 to
each M)
M M
M
Peroxide: O22 O -2 4
2 M
O
Peroxide: O22 O O
O M -2 4
2 bridging (2 to
M M M O
each M)
 Sabhuku Mudavanhu
Intro 25

Oxide, sulfide: O2, S2 M O -2 4

6
M O
Oxide, sulfide: O2, S2 O -2 4
 bridging (2 to
M M each M)
Oxide, sulfide: O2, S2 O -2 6
3 bridging (2 to
M M each M)
M
Amine, phosphine, arsine: M-NR3 0 2
NR3, PR3, AsR3 M-PR3
Amide, phosphide:
M N M P -1 2
NR2, PR2 R R
R R
R 4
M N R
Amide, phosphide: RR -1 4
NR2, PR2 bridging: (2 to
P
each M)
M M
Imido: NR2 R -2 4 (bent)
M N
6 (linear)
M N R
Imido: NR2 R R -2 4 or 6
 bridging (2 or 3 to
N N
each M)
M M M M
Imido: NR2 R -2 6
3 bridging N (2 to
each M)
M M
M
Nitride, phosphide: MN: -3 6
N3, P3
 Sabhuku Mudavanhu
Intro 26

Nitride, phosphide: N N -3 4 or 6
N3, P3,  bridging (2 or 3 to
M M M M each M)
Nitride, phosphide: N -3 6
N3, P3, 3 bridging
M M
M
Nitrosyl: NO+ M N O +1 2
linear form

Nitrosyl: NO M N -1 2
bent form
O
Nitrosyl: NO+ O +1 1 to each
 bridging metal
N
M M
Nitrosyl: NO+ O +1 1 to each
3 bridging metal
N
M M
M
Carbonyl: CO M C O 0 2

Carbonyl: CO O 0 2 to each

,2 mode C metal
M M
Carbonyl: CO O 0 1 to each
 bridging metal
C
M M
Carbonyl: CO O 0 1 to each
3 bridging metal
C
M M
M
 Sabhuku Mudavanhu
Intro 27

Isocyanide: CN-R M C N R 0 2

Isocyanide: CN-R R 0 1 to each

 bridging N metal
C
M M
Alkene: R2C=CR2 R R 0 2
2 bonding mode R C C R

M
Alkyne: RCCR R C C R 0 2 or 4
2 bonding mode

M
Alkyne: RCCR R R 0 2 to each
 bridging C C
metal

M M
Dienes: R2C=CH-CH=CR2 0 4
4 bonding mode
M
Dienes: R2C=CH-CH=CR2 0 2 to each
 bridging metal
M M
Benzene: C6H6 0 6
6 bonding mode
M
Ketones, aldehydes: R 0 2
2 bonding mode R C O

M
Alkyl: CH3, CH2R M CR 3 -1 2
1 bonding mode
 Sabhuku Mudavanhu
Intro 28

Alkyl: CH3, CH2R R R R -1 2

C (1 to
each M)
M M assuming no
agostic M-H
interactions

Aryl: C6H5 -1 2
1 terminal M

Alkenyl (vinyl), alkynyl: M R -1 2

CH=CH2, CCH
1 terminal M

Alkenyl (vinyl): -1 4
CH=CH2 M
2 terminal

Alkenyl (vinyl), alkynyl: M -1 4

CH=CH2, CCH (2 to
,2 terminal M R each M)
M M

Cyclopropenyl: C3H3 -1 4
3 terminal
M
Allyl: C3H5 -1 4
3 terminal
M

Allyl: C3H5 M -1 2
1 terminal

Pentadienyl: C5H7 -1 6
5 terminal

M
Pentadienyl: C5H7 -1 4
3 terminal

M
 Sabhuku Mudavanhu
Intro 29

Pentadienyl: C5H7 M -1 2
1 terminal

Cyclopentadienyl: C5H5 -1 6
5

M
M

Cyclopentadienyl: C5H5 -1 4
3

M
Carbene: =CYR R 0 2
where Y is a substituent M C
capable of  interaction with
the carbene carbon atom Y

Alkylidene: =CR22 R -2 4
where no substituents capable M C
of  bonding to the carbene
carbon atom are present R

Carbene: =CYR or =CR22 Y R -2 2 to each

 bridging metal
C
M M
Carbyne or Alkyidyne: M C R -3 6
CR3

Carbyne or Alkyidyne: R -3 2 to each

CR33 bridging metal
C
M M
M
 Sabhuku Mudavanhu
Intro 30

How do I Figure Out Ligand Charges & Donor #’s ??

(without memorizing that !#&!@%$* entire list)

First, you should learn the charges and donor # for the common
ligands (this will significantly speed up your counting):
Cationic 2e- donor: NO (nitrosyl)
Neutral 2e- donors: PR3 (phosphines), CO (carbonyl), R2C=CR2
(alkenes), RCCR (alkynes, can also donate
4 e-), NCR (nitriles)
Anionic 2e- donors: Cl (chloride), Br (bromide), I (iodide), CH3
(methyl), CR3 (alkyl), Ph (phenyl), H
(hydride)
The following can also donate 4 e- if needed, but
initially count them as 2e- donors (unless they
are acting as bridging ligands): OR (alkoxide),
SR (thiolate), NR2 (inorganic amide), PR2
(phosphide)
Anionic 4e- donors: C3H5 (allyl), O2 (oxide), S2 (sulfide), NR2
(imido), CR22 (alkylidene)
and from the previous list: OR (alkoxide), SR
(thiolate), NR2 (inorganic amide), PR2
Anionic 6e- donors: Cp (cyclopentadienyl), N3 (nitride)

Please note that we are using the Ionic Method of electron-counting.

95% of inorganic/organometallic chemists use the ionic method.
The ionic method assigns formal charges to the metal and ligands in
order to keep the ligands with an even # of electrons and (usually) a
filled valence shell. There is also the neutral method that considers
everything to be neutral. Synthetically, the ionic method makes
more sense and the one that we will use in this course.
 Sabhuku Mudavanhu
Intro 31

Simple Example:

CH3
R3P CO
Re
PR3
CO
1) There is no overall charge on the complex

2) There is one anionic ligand (CH3, methyl group)

3) Since there is no overall charge on the complex (it is neutral),

and since we have one anionic ligand present, the Re metal atom
must have a +1 charge to compensate for the one negatively
charged ligand. The +1 charge on the metal is also its oxidation
state. So the Re is the in the +1 oxidation state. We denote this
in two different ways: Re(+1), Re(I), or ReI. I prefer the Re(+1)
nomenclature because it is clearer. Most chemistry journals,
however, prefer the Roman numeral notation in parenthesis
after the element.

Now we can do our electron counting:

Re(+1) d6
2 PR3 4e-
2 CO 4e-
CH3 2e-
CH2=CH2 2e-
Total: 18e-
 Sabhuku Mudavanhu
Intro 32

Next Electron-Counting Example:

CNCH3 2+
H3CNC
CNCH 3
H3CNC Mo
H3CNC CNCH3
CNCH3
1) There is a +2 charge on the complex
2) The CNCH3 (methyl isocyanide) ligand is neutral, but lets check
the Lewis Dot structure to make sure that is correct:

C NCH3
Nitrogen is normally trivalent, that is, it wants to have 3
chemical bonds to it. When it has 4 bonds, one more than usual,
the nitrogen atom is assigned a formal positive charge. Carbon,
on the other hand, is tetravalent and almost always wants 4
bonds. In isocyanides, however, we only have 3 bonds to the C.
To keep an even number of electrons around the C we add an
extra electron and the carbon gains a formal negative charge.
3) Because there is a +2 charge on the complex and there are all
neutral ligands present, the Mo has a +2 charge & oxidation
state.
Now we can do our electron counting:

Mo(+2) d4
7 CNCH3 14e-
Total: 18e-
 Sabhuku Mudavanhu
Intro 33

More Complicated Ligand Analysis:

H2C M

R2P

H2C M

How do we figure out the charge and electron donor ability of this
weird ligand??

1) Remove the metal atoms and examine the ligand by itself:

H
H
H2C M C

R2P R2P

H2C M H
C
H
Phosphorus is trivalent and since it has four bonds to it, there is a
formal positive charge assigned to the atom. Each carbon is
currently neutral and has an odd electron.
 Sabhuku Mudavanhu
Intro 34

2) We always want the ligand in the ionic method of ligand electron

counting to have an even # of electrons. IF the ligand atom has an
odd # of electrons, add enough electrons to get to an even # (and
usually a filled valence shell). This usually means adding one
electron. In this specific case we have two carbon atoms each which
needs an additional electron to give a lone pair that can donate to
the metal center:
H H
H H
C C
+2e-
R2P R2P

C H
C
H
H H
Adding two electrons to this ligand generates two anionic carbon
donor centers. But remember that we have a positive charge on the
phosphorus atom, which although not involved in bonding to the
metal, is part of the overall charge of the ligand. So two negative
charges and one positive charge (on the phosphorus) yields a net
negative charge on this ligand. Each carbon can donate 2 e- to each
metal center.

This strange ligand is called a phosphorus di-ylide and is a strongly

donating ligand for bridging two metal centers.
 Sabhuku Mudavanhu
Intro 35

More Complicated Metal Compound Analysis:

Me

Rh
PPh3

1) There is no overall charge on the complex

2) There is one anionic ligand (3-C3H5, allyl).
H H
H H +e- H H

H H H H H
H H

H H

H H
H H +e- H H

H H H H
Rule of Thumb: -based carbon ligands that have odd number
attachments to the metal center are usually anionic (except for CO
and CNR [isocyanide] ligands) and donate one more electron than
the number of carbons bonded to the metal center. So our 3-
C3H5, allyl ligand is anionic and donates 4e- to the metal center.
 Sabhuku Mudavanhu
Intro 36

The C5H5Me ligand is NOT a simple anionic cyclopentadienyl

ligand. It is a neutral ligand with two alkenes that each act as
neutral 2e- donors to the metal:

Me

H
If you work out the Lewis Dot structure for this ligand you get an
even # of electrons so there is no need to add an electron to get an
anionic ligand. Note that it is EASY to forget that there is a H on
the Cp carbon that has the methyl group attached if you are not
thinking about organic line notation.
3) Because the complex is neutral and there is one anionic ligand
present, the Rh atom must have a +1 charge to compensate for
the one negatively charged ligand. So the Rh atom is in the +1
oxidation state.

Now we can electron-count:

Rh(+1) d8
PR3 2e-
4-C5H5Me 4e-
3-C3H5 4e-
Total: 18e-
 Sabhuku Mudavanhu
Intro 37

Metal-Metal Bonded Example:

O O

R2 C C R2
P Cl P
Mo Mo
P Cl P
R2 C C R2
O O
At this point we will consider metal-metal (M-M) bonds to be simple
covalent bonds with each metal contributing 1e- to the bond. Most
M-M bonded complexes are symmetrical, which means that one
only has to e- count one metal center. If the metals are different,
however, one does need to figure out each metal center.
The simple rule for M-M bonding is that if you have two metal
atoms next to one another and each has an odd electron-count, you
pair the odd electrons to make a M-M bond. This is electron-
counted as a 1e- donation from one metal to the other.
This example also has -Cl ligands. Bridging ligands with at least 2
lone pairs almost always donate 2e- to each metal center.
Oxidation state determination: There are a total of two anionic
ligands for two metal centers (overall complex is neutral). Thus
each metal center needs to have a +1 oxidation state to balance the
anionic ligands.
Very Common Mistake: Students determining the oxidation state for
complexes with 2 or more metal centers often add up all the anionic
ligands and then figure out the oxidation state for only one of the
metal centers based on this. You need to take into account the
charge (if any) on the complex and divide up the anionic ligand
charges between all the metal centers present. Each metal in the
complex shown above is in the +1 oxidation state – NOT +2.
 Sabhuku Mudavanhu
Intro 38

Now we can electron-count:

Note that each bridging Mo(+1) d5

chloride is donating 2e- to
each Mo center. Although we 2PR3 4e-
only “allocate” one negative CO 4e-
charge for figuring out the 2-Cl 4e-
oxidation state of the Mo atom,
one needs to include in the Sub-total: 17e-
electron-counting the fact that Mo-Mo 1e-
both chlorides are donating TOTAL: 18e-
electrons to each metal center.

This structure is called an edge-sharing bioctahedron (i.e., two

octahedral metal centers sharing a common edge).
 Sabhuku Mudavanhu
Intro 39

Another Metal-Metal Bonded Example:

Me Me
N H2 N
C
Pd Pd
C
N H3 N
Me Me

Ligand analysis: The chelating N ligand is a bis-imine, is neutral,

with each N atom donating 2e-. There are two different bridging
ligands – an anionic CH3 (methyl group) and a dianionic CH22
(carbene or alkylidene). The CH3 only has one lone pair of
electrons, so it has to split these between the two metals (1e- to
each). The CH22 alkylidene ligand, on the other hand, has 2 lone
pairs so it can donate 2e- to each metal center.
Oxidation state analysis: There are a total of 3 negative charges on
the ligands (anionic methyl, dianionic alkylidene) and a positive
charge on the complex. Therefore the two Pd centers must have a
TOTAL of a +4 charge, or a +2 charge (oxidation state) on each.

Pd(+2) d8
2 imines 4e-
-CH3  1e-
-CH22 2e-
Sub-total: 15e-
Pd-Pd 1e-
TOTAL: 16e-

Note that Pd(+2) is generally happy with a 16e- configuration.

 Sabhuku Mudavanhu
Intro 40

Problems in Electron Counting

Re(+1) d6
 6 -benzene 6
Re Mo
 5 -Cp 6
(MeO)3P
18
(MeO)3P

Cl
Ta Ni
Cl PR3
PR3

O
NMe2 N

Cr
Mo N
O
NMe2 N
Me2N O N
NMe2 O

PMe3
Br OC CO
Ti W
Br OC CO
PMe3
 Sabhuku Mudavanhu
Intro 41

Pd Ni

N
O

Mo Mn
C Ph3P
C O
N O
C
O O OMe

Co
Sc OMe Me3 P PMe 3
Me3 P

R
PMe 3
C
CO H Ph2
Cr W CH 2t-Bu
OC C P

OC OR P CH
PMe 3 Ph2
 Sabhuku Mudavanhu
Intro 42

R
C C R O O
O O O C C O
C C C C
Fe ? Fe Fe ? Fe
OC CO
C
C O C
O O
O O
OC C C
CO
O
C
Os
OC
O
C
O
C
Co ? Co
CO
Os ? Os C
H H
O
C C
O O
Br

Au Au
P ? P P ? P
Au Au

CH 3
OR
RO OR
O
Mo Rh
O O
? O R

Mo
R ? R
RO OR R O Rh
O
O
OR O
 Sabhuku Mudavanhu
Intro 43

Why is Electron Counting Important??

One of the complexes drawn in the cycle below is highly unlikely and
studies have shown that it does not exist (as far as we can tell).

Cotton & Wilkinson, 3rd Edition (1972)

 Sabhuku Mudavanhu
Lewis Bases 1

Lewis Base Ligands

Non-carbon donor ligands that have one or more lone pairs of e-

that can be donated into empty orbitals on the metal center.
Although phosphine ligands (PR3) are formally Lewis Base ligands,
their importance in organometallic chemistry is such that we will
treat them separately later.

Halide Donors
Increasing polarizability

Strongest nucleophile
X F , Cl , Br , I for low oxidation state
metals centers
Primary Halides

X X
M X M M
M M
M
2e- terminal 4e- m-bridging 6e- m3 -bridging

The halides are anionic Fluoride is generally NOT a good ligand except
donors that generally only for very high oxidation state metal centers. It is
too electronegative to donate much of its
donate 2e- to a metal center. electron density to a “normal” metal center.
Due to their relatively high
electronegativity they are not especially good -donor ligands.
Although they can theoretically act as -donor ligands, once again,
the higher electronegativity limits them to simple 2e- donor ligands.
 Sabhuku Mudavanhu
Lewis Bases 2
One possible exception to the 2e- donor “rule” when they are
coordinating to a single metal center is for iodide. It is the least
electronegative of the halides (not counting astatine) and is the best
donor group. This is some evidence that iodide is a good enough
donor and has enough orbital extension to act as a 4e- - and -
donor in some cases.
Common Misconception: Since we treat the halides as anionic
halide ligands their relatively high electronegativity does NOT make
them electron-withdrawing ligands as thought of in organic
chemistry. In organic chemistry the halogens are treated as neutral
ligands and as such drain electron density from whatever they are
attached to. But in inorganic and organometallic chemistry they
are anionic and are perfectly happy with that charge. What their
electronegativity does in organometallic chemistry is to NOT make
the halides particularly good donor ligands. As one moves down the
periodic table from F to I, we do see steadily increasing donor
ability as the electronegativity drops.

When halides act as bridging ligands (relatively common) they

donate 2e- to each metal center that they are coordinated to.
 Sabhuku Mudavanhu
Lewis Bases 3

Oxygen Donors

R O
2 O
O THF
tetrahydrofuran

Alkoxides Oxide Ethers

2 or 4e- donor 4 or 6e- donor 2e- donor
Terminal Terminal Typically
Bridging Bridging weak donor
Triply bridging Triply bridging
Quad bridging

R O M
O
C R M R
O O
O O
2 -chelating 4e- 1 2e- mode
Carboxylates
2 or 4e- donor O M
1-terminal R m-bridging
2-terminal
Bridging O M

H
R R Acetoacetonates (acac) R
2 or 4e- donor O
O O H

M Unusual C-bonded M
acac O
R
 Sabhuku Mudavanhu
Lewis Bases 4

Sulfur Ligands
2e- or 4e- Terminal
R S 4e- Bridging Easily oxidized
6e- Triply bridging to R-S-S-R
Thiolates
Mercaptides
Thiolates are powerful bridging ligands, particularly for low-
oxidation state metal centers. The lower electronegativity relative
to oxygen means that thiolates are also better donors.

2 4e- Terminal M S Relatively

S 4e- Bridging M S rare
6e- Triply bridging
Sulfide 8e- Quad bridging

Sulfides (and thiolates) are extremely effective bridging ligands and

play a critically important role as such in bioinorganic chemistry:

Fe/S Cubanes S 2-
RS SR
2- Fe Fe
SR RS S
SR
RS S Fe
R
Fe S S
R
3-
S
Ferredoxins
Fe S Fe
S S
S Fe
SR Fe Fe
RS SR
S S
2Fe(+2) R
S R

2Fe(+3)
 Sabhuku Mudavanhu
Lewis Bases 5

Nitrogenase
The nitrogenase enzyme catalyzes the extremely difficult reaction:
N2 + 8H+ + 8e- 2NH3 + H2
The conversion of atmospheric N2 into NH3 is a marvel of catalysis
and provides the plant with its own fertilizer. In the Haber catalytic
process for converting N2 + 3H2 into NH3, over 400ºC and 400 atm
of H2/N2 pressure are required along with a heterogeneous Fe
catalyst. Nitrogenase does this at
room temperature and pressure.
Nitrogenase, shown to the right, requires a
steady source of electrons. The reaction
requires the addition of 8 electrons for each
nitrogen molecule that is split into two NH3
molecules and one “wasted” H2. The Fe
protein (green) uses the breakage of ATP to
pump these electrons into the MoFe protein
(blue-purple). Two molecules of ATP are
consumed for each electron transferred.
The active catalytic site in the enzyme
is believed to be this unusual Fe/Mo/S
cluster – the central atom is believed to be a nitride (N3), see Science,
2002, 297, 1696-1700.

S Fe Fe S R
O
S N S
RS Fe Fe Fe Mo O
O
Fe S Fe
N(his)
S S S
 Sabhuku Mudavanhu
Lewis Bases 6

Nitrogen Ligands

In general, alkylated amines are not particularly good

ligands. This is mainly due to the relatively short N-C
N
R
bond distances and the stereoelectronic problems
R generated from this.
R
Chelating amines have less steric problems and are
better ligands for transition metal centers. Primary and secondary
amines, however, are susceptible to oxidations:
H2 2+ H 2+
N N
- 4e-
M M + 4H+
M=Ru
N N
H2 H

Di-imine Complex

Tertiary amines, on the other hand, are quite stable and not easily
oxidized.

Me Me chelate effect helps

N N coordinate metals more strongly
Me Me

TMEDA = tetramethylethylenediamine

Perhaps the most famous neutral nitrogen donor ligand is

bipyridine or bipyridyl, almost universally abbreviated bipy.
Phenanthroline is a more rigid version of bipy that forms even
stronger metal chelates.

N N N N
Bipy = Bipyridine Phen = phenanthroline
 Sabhuku Mudavanhu
Lewis Bases 7
The most famous bipy complex is [Ru(bipy)3 ]2+, N 2+
which has an extremely rich photoredox
chemistry. There are probably over 1000 N
N Ru N
papers concerning [Ru(bipy)3]2+.
N
Bipy (and its related systems) can stabilize N
multiple oxidation states on metal complexes:
[Cr(bipy)3]3+ [Cr(bipy)3]1

Inorganic Amides
Strong Base & Nucelophile
Terminal (2 or 4e-) donor
N 4e- Bridging donor
R
R
The lone pairs in an amide are about 2eV higher in energy than in
OR. This makes an amide a considerably stronger donor.
Typical formation reaction:
MXn + nLiNR2 M(NR2)n + nLiX
Amides that act as 2e- donors have pyramidal geometry (sp3-like)
with a free lone pair, while amides that donate 4e- have a trigonal
planar (sp2-like) geometry. There are, of course, in-between
structural cases that indicate intermediate bonding situations.

R
M N M N
R R
R
2e- donor 4e- donor
pyramidal geometry trigonal planar
 Sabhuku Mudavanhu
Lewis Bases 8
Alkyl-Imido (nitrene) Ligand
R R

 4e- or 6e- Terminal N N
R N 4e- Bridging 
6e- Triply bridging M M
Imido (nitrene)
Bent Linear
(nucleophillic (electrophillic
nitrogen) nitrogen)

In the bent mode the imido ligand is formally only a 4e- donor, while
in the linear mode it donates 6e- to the metal center. As with the
other ligands we have seen that can donate variable numbers of
electrons to the metal center, you initially count it as a 4e- donor
and then boost it up to 6e- if you need to increase the electron count
on the metal to get up to 16 or 18 e-.
Some examples:
Me

N N N
Ph 3
P
Os Ta Cl Re Cl
O O R2N NR2 Ph3P
O NR 2 Cl
As one moves to the right-hand
side of the periodic table, one tends
to get less M-L multiple bonding
As with amides, you can have intermediate cases where the bending
of the alkyl group is in-between linear and bent. It is difficult to
predict when the imido ligand will act as a 4e- or 6e- donor. So long
as you give me a reasonable electron count I will not be picky about
whether you use 4e- or 6e-. If you use 6e- you should realize that
the imido and alkyl group should be drawn linear.
 Sabhuku Mudavanhu
Lewis Bases 9
Tris(pyrazolyl)borate Ligand
H  Anionic
R  6e- donor
B R  coordination via
the three lower
N N N nitrogen centers
 Moderate donor
 Steric effects
N N N adjusted via R
groups
R R
M
The tris(pyrazolyl)borate (Tp) ligand has become extremely popular
in the last decade and is sometimes called the inorganic Cp ligand.
It is anionic and is a 6e- donor when all three nitrogens are
coordinated to a metal center, just like Cp-.
It is considerably bulkier (much bulkier if one uses large bottom R
groups) and, due to the higher nitrogen electronegativity, it is not as
good a donor relative to Cp.
When drawing the ligand, you can abbreviate it as follows:
R
B

N
N N
M
Most inorganic and organometallic chemists will understand what
you are talking about with this simplified drawing.
 Sabhuku Mudavanhu
Lewis Bases 10
A Few Biologically Important N-Ligands

N
N

N N N N
N N
H

imidazolate pyrimidine purine

2 3

1 4
NH N

N HN
8 5

7 6

Porphine
(metalloporphyrin when bound to a metal)

Protein
S
S Protein S Protein

N N N N
Fe Fe
N N N N

HOOC COOH HOOC

HOOC
Cytochrome-C Fe-protoporphyrin IX
 Sabhuku Mudavanhu
Carbonyls 1

Carbonyl Ligands

Metal carbonyls form one of the oldest (and important) classes of

organometallic complexes. Most metal carbonyls are toxic!
Examples of neutral, binary metal carbonyls:
4 5 6 7 8 9 10 11
Fe(CO)5 Co2(CO)8
Ti V(CO)6 Cr(CO)6 Mn2(CO)10 Fe2(CO)9 Co4(CO)12 Ni(CO)4 Cu
Fe3(CO)12
Nb Mo(CO)6 Tc2(CO)10 Ru(CO)5 Rh4(CO)12
Zr Ru3(CO)12 Rh6(CO)16 Pd Ag
Hf Ta W(CO)6 Re2(CO)10 Os(CO)5 Ir4(CO)12 Pt Au
Os3(CO)12
 Sabhuku Mudavanhu
Carbonyls 2

Physical Properties of Selected Metal Carbonyls

Color mp °C Sym IR CO cm1 Misc
V(CO)6 blue-black 70(d) Oh 1976 paramagnetic, S = 1/2

Cr(CO)6 white subl Oh 2000 Cr-CO = 1.91 Å, air-stable

Mo(CO)6 white subl Oh 2004 Mo-CO = 2.06 Å, air-stable

W(CO)6 white subl Oh 1998 W-CO = 2.06 Å, air-stable in

solid state.

Mn2(CO)10 yellow 154 D4d 2044, 2013, 1983 Mn-Mn = 2.89 Å, bond is easily
broken.

Tc2(CO)10 white 160 D4d 2065, 2017, 1984 Tc-Tc = 3.03 Å

Re2(CO)10 white 177 D4d 2070, 2014, 1976 Re-Re = 3.04 Å

Fe(CO)5 yellow -20 D3h 2034, 2013 bp = 103°C, toxic, Fe-CO (ax) =
1.81 Å, Fe-CO (eq) = 1.83 Å, h
produces Fe2(CO)9

Fe2(CO)9 gold d D3h 2082, 2019, 1829 Fe-Fe = 2.46 Å, insoluble in

plates most solvents except for THF
where is dissociates to produce
Fe(CO)4 + Fe(CO)5

Fe3(CO)12 green d low complex

Ru(CO)5 colorless -16 D3h 2035, 1999 unstable, forms Ru3(CO)12

Ru3(CO)12 orange 150(d) D3h

Os(CO)5 colorless 2 D3h 2034, 1991 v. unstable, forms Os3(CO)12

Os3(CO)12 yellow D3h

Co2(CO)8 orange- 51(d) D3d 2107, 2069, 2042, solid state structure has 2 -CO’s
red 2031, 2023, 1991 (1886, 1857 cm1). Solution
structure is unbridged. Co-Co =
2.54 Å in solid-state.

Rh4(CO)12 red C3v 3 -CO’s around one triangular

Rh3 face.

Ni(CO)4 colorless -25 Td 2057 bp 34°C, highly toxic, CO’s

quite labile, Ni-CO = 1.84Å
 Sabhuku Mudavanhu
Carbonyls 3

Molecular Orbital Diagram for CO:

A simple MO diagram for CO is shown above. The highest occupied

molecular orbital (HOMO) is indicated by the pair of electrons. This is the
5 lone pair orbital mainly centered on the carbon and weakly anti-
bonding with respect to the C-O bond (although that isn’t too clear from
the orbital contour plot). The weak C-O antibonding nature of this MO,
however, is clearly seen in the experimental data presented below. The
LUMO is strongly * antibonding and is low enough in energy to act as a
good acceptor orbital for interacting with filled d-orbitals on metals.

Experimental Data Supporting Nature of MO’s in CO

Species Config C-O Å CO cm1 Comment
CO (5)2 1.13 2143
CO+ (5)1 1.11 2184 5 MO is weakly antibonding
CO* (5)1(2)1 S 1.24 1489 2 MO is strongly antibonding
T 1.21 1715
 Sabhuku Mudavanhu
Carbonyls 4

Three types (two of which are important) of CO-Metal bonding

interactions:

M-C bond: increases increases increases

C-O bond: increases decreases decreases
CO freq: increases decreases decreases

Carbonyl IR Stretching Frequencies

 The position of the carbonyl bands in the IR depends mainly on the
bonding mode of the CO (terminal, bridging) and the amount of
electron density on the metal being -backbonded to the CO.
 The number (and intensity) of the carbonyl bands one observes
depends on the number of CO ligands present and the symmetry of the
metal complex. There are also secondary effects such as Fermi
resonance and overtone interactions that can complicate carbonyl IR
spectra.
 Sabhuku Mudavanhu
Carbonyls 5
Bonding Modes:
As one goes from a terminal CO-bonding mode to 2-bridging and
finally 3-bridging, there is a relatively dramatic drop in the CO stretching
frequency seen in the IR.
O O
O C O C M C C
M M
M M M
free CO terminal mode 2 bridging 3 bridging

CO IR (cm -1 ) 2143 2120 - 1850 1850 - 1720 1730 - 1500

(for neutral metal complexes)

Note that these ranges are typical for “neutral” transition metal
complexes with an average amount of electron density on the metal center
(see discussion below). Bridging carbonyls tend to have weaker and
broader IR bands.

Effect of Electron Density on Metal:

As the electron density on a metal center increases, more -back-
bonding to the CO ligand(s) takes place. This futher weakens the C-O
bond by pumping more electron density
dx Complex CO cm1
into the formally empty carbonyl *
orbital. This increases the M-CO bond free CO 2143
strength making it more double-bond- d10 [Ag(CO)]+ 2204
like, i.e., the resonance structure Ni(CO)4 2060
M=C=O assumes more importance. [Co(CO)4] 1890
This can clearly be seen on the table
[Fe(CO)4]2 1790
to the right that illustrates the effect of
charge and electronegativity on the [Mn(CO)6]+ 2090
amount of metal to CO -backbonding d6 Cr(CO)6 2000
and the CO IR stretching frequency. [V(CO)6] 1860
 Sabhuku Mudavanhu
Carbonyls 6

Shown below is another example of the dramatic effect on the CO IR

stretching frequencies on reducing Fe2(-PPh2)2(CO)6 by 2 electrons to
form the dianionic complex [Fe2(-PPh2)2(CO)6]2. The average CO
frequency shifts almost 150 cm1 to lower energy on reduction.
Ph2 Ph 2
P P
Ph 2 2-
OC CO O O
Fe Fe C P C
OC CO
C C OC
Fe Fe CO
O O C P C
O Ph 2 O
2100 2000 1900 1800
Wavenumbers (cm-1 )

The carbonyl region in the IR spectrum can be very distinctive and useful
for help in assigning structures and for indicating the relative amount of
electron density present on the metal (dppm = Ph2PCH2PPh2, Ph groups
not shown on structural drawings below):
O
OC C CO
Ni2(  -CO)(CO) 2(dppm) 2 Ni Ni
P P

-CO +CO P P

P P
Ni 2(CO) 4(dppm) 2 OC CO
Ni Ni
OC CO
P P

-CO +CO

P P
2 Ni(CO) 3(  -dppm)
1 OC
Ni
OC
C
O

2000 1900 1800 1700

Wavenumbers (cm-1 )
 Sabhuku Mudavanhu
Carbonyls 7
Ligand Donation Effects:
The ability of the ligands on a metal to donate electron density to the
metal center certainly has considerable effect on the absolute amount of
electron density on that metal. This, in
turn, naturally effects the CO IR Complex CO cm1
stretching frequencies in metal Mo(CO)3(PF3)3 2090, 2055
carbonyl complexes. Ligands that are Mo(CO)3(PCl3)3 2040, 1991
trans to a carbonyl can have a Mo(CO) [P(OMe) ] 1977, 1888
3 33
particularly large effect on the ability
Mo(CO)3(PPh3)3 1934, 1835
of the CO ligand to effectively -
backbond to the metal. For example 2 Mo(CO)3(NCCH3)3 1915, 1783
trans -backbonding ligands will Mo(CO)3(triamine)3 1898, 1758
partially compete for the same d-orbital Mo(CO)3(pyridine)3 1888, 1746
electron density, weakening each
others net M-L -backbonding.

When the trans ligand is a -donating ligand, this can increase the M-CO
bond strength (more M=C=O character) by allowing unimpeded metal to
CO -backbonding. Pyridine and amines are not that strong -donors, but
they are even worse -backbonding ligands. So the CO has virtually no
competition for -backdonation.

Based on CO IR stretching frequencies, the following ligands can be

ranked from best -acceptor to worst:
NO+ > CO > PF3 > RNC > PCl3 > P(OR)3 > PR3 > RCN > NH3
 Sabhuku Mudavanhu
Carbonyls 8

Semi-Bridging Carbonyls:
Unsymmetrical bridging form. * system accepts
~ 150
O electron density from second metal center. Usually
accompanied by distortions away from a linear M-
C CO (180°) or a symmetrically bridging CO (120°).
Typical M-CO angle around 150° (but with consider
M M variations).
Example: Substituting 2 carbonyls in Fe2(-
CO)3(CO)6 with a bipy ligand leads to a considerable change in the
structure, particularly in the bridging CO region. The better -donating
bipy ligand increases the e density on that Fe atom. This generates an
asymmetrically charged complex. The higher partial negative charge on
the bipy-substituted Fe center can be reduced by dumping some of it
specifically into the * orbital of one of the bridging carbonyls, turning it
into a semi-bridging CO.

filled Fe d orbital
O
O O
C C C
Cotton & Troup
JACS, 1974, 96, 1233

C
Fe Fe
O N
C C
N
O O

CO * empty antibonding
acceptor orbital
 Sabhuku Mudavanhu
Carbonyls 9

/ Bridging CO:

O O O
C C C
M M M M M M
M M
This is where the CO not only acts as a traditional -donor/-acceptor to
one or more metal centers, but also as a -donor to additional metals.
This will occur for more electron deficent metal complexes where the
metal centers have less need to -backbond to the carbonyl, but have the
empty orbitals to accept electron density from the carbonyl -system. The
CO ligand here can act as a 4 or 6 electron donor!

Problem: Consider the example below, do you think that the bridging
CO should act more as a -donor or -acceptor?

CO acting as -donor or -acceptor?

1.30Å
2.22Å 2.25Å O
O
O C C 1.97Å
C
Nb Nb Cp
Cp
C Nb C
O
O
Cp C C
O
O
Herrman & coworkers
JACS, 1981, 103, 1692
 Sabhuku Mudavanhu
Carbonyls 10
Problem: Which of the following metal carbonyl IR spectra
represents the compound with the least amount of electron density on
the metal center? Briefly discuss the reasoning for your choice.
Which compound will lose CO the easiest?

Problem: Which of the following metal carbonyl compounds will

have the highest CO stretching frequency in the IR? Why? Will this
be the most electron-rich or deficient compound?
a) CO
b) CO
F CO Br CO
Ir Ir
F CO Br CO
F Br

c) CO
Me2N CO
Ir
Me2N CO
NMe2
 Sabhuku Mudavanhu
Phosphines 1

Phosphine Donors

Because of the three R-groups on the phosphine ligand and the overall
tetrahedral coordination geometry it is the most versatile of the neutral
2-electron donor ligands. Variation of the three R-groups can effect:
 large changes in the donor/acceptor properties of the phosphine (from
excellent donor/poor -acceptor to poor donor/excellent -acceptor)
 large changes in the steric profile of the phosphine (from fairly small to
enormous)
 generation of a large number of polydentate polyphosphines (bis-, tris-,
tetra-, penta-, and hexaphosphine ligands are all known) that can adopt
specific coordination geometries (cis-enforcing, facial tridentate,
bridging, bridging and chelating, etc.)
R2
P PR2
M M
R2P
R P M
R2 R P P
PR2
R
M( -tripod)
3
racemic-M2(P4)
facial coordinating binucleating phosphine
able to bridge and chelate 2 metals
 Sabhuku Mudavanhu
Phosphines 2
Tolman’s Cone Angle and Electronic Parameter
In 1977 Chad Tolman (Dupont Chemicals) published a classic review
article covering methods that he developed for ordering a wide variety
of phosphine ligands in terms of their electron-donating ability and
steric bulk (Chemical Reviews, 1977, vol 77, pages 313-348).
The electron-donating ability of a phosphine ligand was determined by
reacting one equivalent of the phosphine (monodentate only) with
Ni(CO)4 to make a Ni(CO)3(phosphine) complex. He then measured
the carbonyl CO IR stretching frequency (the very sharp a1 high energy
mode) of the Ni(CO)3(phosphine) complex. The more electron density
the phosphine ligand donated to the metal center, the more -back-
bonding occurred to the carbonyl ligands, weakening the CO triple
bond, thus lowering the CO IR stretching frequency.
Lowest CO stretching O
frequency: C
most donating OC Highest CO stretching
frequency:
phosphine R least donating
phosphine
C
O (best -acceptor)

The size or steric bulk of a phosphine ligand was determined from

simple 3-D space-filling models of the phosphine ligands. Tolman
coined the name cone angle () to indicate the approximate amount of
“space” that the ligand consumed about the metal center.

cone angle 
M
 Sabhuku Mudavanhu
Phosphines 3
Phosphine Donor Ability Ranked by
Tolman’s Electronic Parameter  (most donating to least)
PR3 mixed P(OR)3 PX3 , cm1
P(t-Bu)3 2056.1
PCy3 2056.4
P(o-OMe-C6H4)3 2058.3
P(i-Pr)3 2059.2
PBu3 2060.3
PEt3 2061.7
PEt2Ph 2063.7
PMe3 2064.1
PMe2Ph 2065.3
P(p-OMe-C6H4)3 PPh2(o-OMe-C6H4) 2066.1
PBz3 2066.4
P(o-Tol)3 2066.6
P(p-Tol)3 PEtPh2 2066.7
PMePh2 2067.0
P(m-Tol)3 2067.2
PPh2(NMe2) 2067.3
PPh2(2,4,6-Me-C6H2) 2067.4
PPhBz2 2067.6
PPh2(p-OMe-C6H4) 2068.2
PPh2Bz 2068.4
PPh3 2068.9
PPh2(CH=CH2) 2069.3
P(CH=CH2)3 PPh2(p-F-C6H4) 2069.5
PPh(p-F-C6H4)2 2070.0
P(p-F-C6H4)3 2071.3
PPh2(OEt) 2071.6
PPh2(OMe) 2072.0
 Sabhuku Mudavanhu
Phosphines 4
PPh(O-i-Pr)2 2072.2
P(p-Cl-C6H4)3 2072.8
PPh2H 2073.3
PPh(OBu)2 2073.4
P(m-F-C6H4)3 2074.1
PPh(OEt)2 2074.2
PPh2(OPh) 2074.6
PPh2(C6F5) 2074.8
P(O-i-Pr)3 2075.9
P(OEt)3 2076.3
PPhH2 2077.0
P(CH2CH2CN)3 2077.9
P(OCH2CH2OMe)3 2079.3
P(OMe)3 2079.5
PPh(OPh)2 2079.8
PPh2Cl 2080.7
PMe2CF3 2080.9
P(O-2,4-Me-C6H3)3 PH3 2083.2
P(OCH2CH2Cl)3 2084.0
P(O-Tol)3 2084.1
P(OPh)3 2085.3
P(OCH2)3CR 2086.8
P(OCH2CH2CN)3 2087.6
P(C6F5)3 2090.9
PCl3 2097.0
PF3 2110.8

Problem: Order the following phosphines from strongest to

weakest  donor:
P(OEt)3 PPh3 PPr3 PCl3 PPh(OMe)2
 Sabhuku Mudavanhu
Phosphines 5
Phosphine Steric Bulk Ranked by
Tolman’s Cone Angle  (smallest to largest)
PR3 mixed P(OR)3 PX3  (°)
PH3 87
PPhH2 P(OCH2)3CR 101
PF3 104
Me2PCH2CH2PMe2 P(OMe)3 107
P(OEt)3 109
P(CH2O)3CR 114
Et2PCH2CH2PEt2 115
P(OMe)2Ph or Et 115
PPh(OEt)2 116
PMe3 118
Ph2PCH2PPh2 121
PMe2Ph 122
PMe2CF3 PCl3 124
Ph2PCH2CH2PPh2 125
PPh2H P(OPh)3 128
P(O-i-Pr)3 130
PBr3 131
PEt3, PPr3, PBu3 PPh2(OMe) 132
PPh2(OEt) 133
PEt2Ph, PMePh2 136
P(CF3)3 137
PEtPh2 140
Cy2PCH2CH2PCy2 142
PPh3 145
PPh2(i-Pr) 150
 Sabhuku Mudavanhu
Phosphines 6

PPh2(t-Bu) 157
PPh2(C6F5) 158
P(i-Pr)3 160
PBz3 165
PCy3 PPh(t-Bu)2 170
P(O-t-Bu)3 175
P(t-Bu)3 182
P(C6F5)3 184
P(o-Tol)3 194
P(mesityl)3 212

Problem: Order the following phosphines from smallest to largest:

P(OEt)3 PPh3 PPr3 PCl3 PPhCy2

Problem: Order the following phosphines from best -acceptor to

worst -acceptor:
P(OEt)3 PPh3 PPr3 PCl3 PPhCy2
 Sabhuku Mudavanhu
Phosphines 7
Commonly Used Monodentate Phosphines:

PPh3 (145°, medium donor), triphenylphosphine, tpp “The KING”

 air-stable, white crystalline material, no odor to speak of

Increasing -Donor Ability:

PMePh2 (136°), PMe2Ph (122°), PMe3 (118°), PEt3 (132°)
P(Cy)3 (170°) tricyclohexylphosphine, P(t-Bu)3 (182°)
 the alkyl phosphines are strong -donors; usually colorless liquids,
somewhat to very air-sensitive, horrible smelling (unless very high
MW and non-volatile)

Poor -Donors, Good -Acceptors:

Phosphites: P(OMe)3 (107°), P(OEt)3 (110°), P(OPh)3 (128°)
 phosphites are relatively poor -donors, but can be fairly good -
acceptor ligands (about half as good as CO); low MW ones are
usually colorless liquids, higher MW compounds are white solids;
usually air-stable but moisture sensitive; sometimes sweet smelling

PF3 (104°) } v. poor donor; strong -acceptor, almost as good as CO

 Sabhuku Mudavanhu
Phosphines 8
Commonly Used Polydentate Phosphines:

Ph2P PPh2 A-Frame bimetallic

Ph2P PPh2 O
C C
O

Rh Rh Rh2(-S)(CO)2(dppm)2
dppm (121°)
diphenylphosphinomethane
S Kubiak & Eisenberg
JACS, 1977, 99, 6129
bis(diphenyl)phosphinomethane Ph2P PPh2
bridging ligand

Ph2P typical P-M-P angle for a

86.9° 5-membered chelate ring
PPh2
Ph2P PPh2 82-87°
dppe (125°) NiCl2(dppe)
diphenylphosphinoethane Ni
bis(diphenyl)phosphinoethane van Koten, et al
chelating ligand Cl Cl Acta Crys. C, 1987, 43, 1878
95.5°

Me2P Ph2P PPh2

PMe2
dmpe (107°) dppp (127°) typical P-M-P
dimethylphosphinoethane diphenylphosphinopropane angle for a
bis(dimethyl)phosphinoethane bis(diphenyl)phosphinopropane 6-membered
chelating ligand chelating ligand chelate ring
88-92°
electron-rich, strong donor forms 6-membered rings
 Sabhuku Mudavanhu
Phosphines 9
Some Other Polydentate Phosphines:
facial coordinating mode
Te Te
Vaira & coworkers
Angew. Chem. Int. Ed., 1987, 26, 916
Ni
PPh
Ph2P
Ph
P Ph2P
Ph2P PPh2
triphos
bis(diphenylphosphinoethyl)phenylphosphine
bis-chelating ligand Ph2P +

Cl Ni P Ph
Bertinsson
Acta Crys. C., 1983, 39, 563

planar coordinating mode Ph2P

Ph2
P Cl Ph2P

Me P M Cl Cr CH3
P
Ph2 Ph2

PPh2 Cl Ph2P

tripod Jones & coworkers

Inorg. Chem., 1986, 25, 1080
tris(diphenylphosphinoethyl)methane
bis-chelating ligand
facial coordination
 Sabhuku Mudavanhu
Phosphines 10

Ph2 Ph2 2+
109°
Ph P P
P PPh2
Ph2P P Pt 84°
Ph
P P
tetraphos-1
1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphophadecane Ph Ph
tris-chelating or binucleating (bridging) ligand
Bruggeller & coworkers
Acta Crys. C., 1990, 46, 388

+ Ph
PPh

P PPh2
PhP P
Fe Br Ph2P
Pt Pt
P Ph Cl
Ph2 Cl
P Cl
Ph2 Cl

Bacci & coworkers Bruggeller & coworkers

Inorg. Chem., 1984, 23, 2798 Inorg. Chim. Acta, 1992, 197, 75

PPh2 PPh2
PPh2
P P Co P(OMe)3

PPh2 PPh2

tetraphos-2 PPh2
tris(diphenylphosphinoethyl)phosphine
tris-chelating ligand Meek & coworkers
Inorg. Chem., 1983, 25, 616
facial coordination

Polyphosphine review: Cotton & Hong, Progress in Inorg. Chem., 1992, 40, 179-289.
 Sabhuku Mudavanhu
Phosphines 11
Some Structural Issues
Phosphines have only been characterized as simple 2 e donating,
terminal-only ligands. No true x-bridging monophosphines are known
(although bridging phosphides, PR2, are very common).
Phosphines generally tend to orient trans to one another in order to
minimize steric interactions (especially true for bulky PR3). Chelating
bisphosphine ligands are used to enforce cisoidal coordination
geometries when needed.
Some typical first row M-PR3 average bond distances:
Ti-P 2.6 Å
V-P 2.5 Å
Cr-P 2.4 Å
Ni-P 2.1 Å
M-P distances decrease due to the contraction of the metal atom radius
as one proceeds to the right and the atoms become more electronegative.
Distances also decrease due to stronger M-P bonding as one moves to
the right across the transition metal series (later transition metals are
“softer” and prefer bonding to phosphines).
M-P bonds are the strongest for alkylated phosphine ligands bonding to
a neutral or monocationic middle to later transition metal center that is
electron-deficient. High oxidation state early transition metals are too
“hard” to have very effective bonding to most phosphines, although
more and more early transition metal phosphine complexes are being
characterized and found to be reasonably stable.
 Sabhuku Mudavanhu
Phosphines 12
Metal centers that are too electron-rich will generally not want to have a
strong electron-donating alkylated phosphine coordinated, this leads to
weaker M-P bonding and more likely phosphine dissociation. One
example is Rh2(-CO)(CO)4(P4), shown below, that rearranges to form
the asymmetric ,3,1-P4 coordinated dimer, shown to the right, when
one CO ligand is lost:
O O Ph
C C Ph
P P
Et 2P CO -CO Et 2
Rh Rh P CO
OC C PEt2 Rh Rh
O +CO Et 2P CO
P P Ph C C
O O
Ph
This is a fully reversible CO and temperature dependent equilibrium.
The asymmetric dimer, which has been structurally characterized, can
be considered to be zwitterionic: one cationic Rh(+1) center that has 3
phosphines coordinated and an anionic Rh(1) pseudo-tetrahedral center
that has 3 -accepting CO ligands. One of these CO’s is acting as a
semi-bridging ligand -donating some electron density to the other
formally cationic square-planar rhodium.
C' Rh 2 (CO) 3 (  -CO)(3,1 -et,ph-P4)
C11 P1
Rh1-Rh2 = 2.9052(3) Å P2-Rh2-P4 = 177.64(4)°
C31
P3 Rh1-C2 = 2.374(4) Å Rh1-C2-Rh2 = 84.0(1)°
C12 C32 Rh2-C2 = 1.942(3) Å

P4 Rh2 C4 O4
P2
Rh1 C3
C1
C2
O3
O1

O2
 Sabhuku Mudavanhu
Phosphines 13
Bond Length vs. Bond Strength
Aroney & coworkers (Inorg. Chem., 1995, 34, 330-336) claimed that
the shorter Cr-PCl3 bond in Cr(CO)5(PCl3) vs. Cr(CO)5(PMe3) was a
result of strong -backbonding. They did NOT make any statements
about bond strengths, but implied that the Cr-PCl3 bond is shorter and,
therefore, stronger than the Cr-PMe3 bond.
Cr(CO)5(PR3 )
PCl3 PMe 3

Cr-P = 2.24Å Cr-P = 2.37Å

Cr-C = 1.90Å Cr-C = 1.85Å

C-O = 1.14Å C-O = 1.15Å

Let’s compare the P lone pair orbital for free PCl3 and PMe3 ligand,
which is the highest occupied molecular orbital (HOMO):

PCl3 PMe3

HOMO energy = 8.36 eV 6.23 eV

 Sabhuku Mudavanhu
Phosphines 14

Note the higher energy (better  donor) and greater orbital extent of the
P lone pair on PMe3 (right plot). This means that the PMe3 ligand does
not have to get as close to the metal center as PCl3 in order to get good
bonding overlap.
Below are shown single-point (no geometry optimization) DFT
calculations on Cr(CO)5(PCl3) and Cr(CO)5(PMe3) based on their
crystal structures, followed by calculations with the phosphine ligands
dissociated (4.0 Å separation) to see the relative change in energies.

Note the clear-cut -backbonding between the PCl3 and the Cr center,
while there is just a trace of -backbonding in the Cr-PMe3 bond. Note
that the Cr-CO ligand trans to the PCl3 has a bit more orbital extent
indicating a little more p-backbonding ability.
The difference in total energies represents the difference in PMe3 vs.
PCl3 bond energies:
E Bond dissociation =
(E(bonded-unbonded)PMe3) - (E(bonded-unbonded)PCl3)
E Bond dissociation = 6.8 Kcals (PMe3 system having stronger bonding)
 Sabhuku Mudavanhu
Phosphines 15
Further Test: Examine PCl3 vs. PMe3 bonding to a d0 metal center:
TiCl4(PCl3) and TiCl4(PMe3).
In this d0 system the lack of any -
backbonding possibilities and 4.63 Å 2.18 Å
good Ti-Cl bonding favored
complete dissociation of the poor
 donating PCl3 ligand. The far
better PMe3 -donor, on the other
hand, bonds nicely to the Ti(+4) d0
center.
2.69 Å 2.24 Å
Bond Length/Strength
conclusions: For most systems a
shorter bond usually indicates a
stronger bond when comparing
similar atoms and bonds.
For metal-ligand complexes there can be exceptions to this when the
ligands in question have fairly different donor/acceptor properties. In
Cr(CO)5(PCl3) the shorter bond distance relative to Cr(CO)5(PMe3)
arises due to the combination of a contracted lower energy P orbitals
and moderate to significant -backbonding. The DFT calculations
indicate that the PMe3 complex has stronger M-P bonding despite the
significantly longer Cr-P distance (2.37Å vs. 2.24Å). The greater PMe3
lone pair orbital extent and higher energy (better donor ability) produces
a strong M-P -bond with a longer bond distance relative to the PCl3.
In order to get effective -backbonding in the Cr-PCl3 complex, the
bond distance has to be shorter to get optimum orbital overlap. In the
Ti(+4) d0 system the PCl3 ligand did not form a Ti-P bond, even though
TiCl4 only has an 8e- count, due to the lack of -backbonding and
weaker -bonding ability relative to PMe3.
 Sabhuku Mudavanhu
Phosphines 16

Problem: For each of the following pairs of metal complexes,

which should have the highest average carbonyl IR
stretching frequency.

a) CpFeBr(CO)2 -or- CpRuCl(CO)(PMe3)

b) MnCl(CO)5 -or- Cr(CO)6

c) (3-allyl)Co(PPh3)(CO)2 -or- (3-allyl)Co(PMe3)(CO)2

d) [Rh(CO)2(P(OPh)3)2]+ -or- Rh(CH3)3(CO)(dmpe)

e) Mo(CO)4(PMe3)2 -or- W(CO)4{P(OMe)3}2

f) CpRe(CO)2{P(OMe)3} -or- Hf(O)Cl2(CO)(PEt3)2

 Sabhuku Mudavanhu
Phosphines 17
31P NMR Spectroscopy
The 31P (P-31) nucleus has a nuclear spin of ½ and is 100% abundant!
This makes it functionally equivalent to the 1H nucleus: therefore, 31P
NMR is an extremely valuable tool in studying phosphines in general,
and M-PR3 complexes in particular. This is another reason why
phosphines are such valuable ligands.
The typical chemical shift region for 1H NMR spans about 20 ppm. The
31P NMR chemical shift region, however, is much larger and can span
almost 1000 ppm (including phosphide ligands)! Chemical shifts for
some phosphines are listed below:

Ligand Chemical Shift (ppm) Ligand Chemical Shift (ppm)

PCl3 220 H3PO4 0 (reference)
PMeCl2 191 P(CF3)3 -2
PCy(OBu)2 184 PPh3 -6
P(OMe)3 140 PEt3 -20
P(OPh)3 126 NaPPh2 -24
PEt2Cl 119 PMePh2 -28
PPh2(OMe) 115 PPr3 -33
PF3 97 PMe2Et -50
PMe2Cl 96 PMe3 -62
PMe2(O-t-Bu) 91 P(CN)3 -135
O=P(CH2OH)3 45 PH3 -238
O=PMe3 36 KPH2 -255
 Sabhuku Mudavanhu
Phosphines 18

It is important to note that the positive and negative convention for

chemical shifts for 31P NMR compounds changed in the early 1970’s.
In these older references, free PMe3 would be listed with a +62 ppm
chemical shift.
Chelate Ring Effects:
The presence of chelate rings can have a significant effect on the 31P
NMR chemical shift position of M-P complexes (Cf., Garrou, Chem.
Rev., 1981, 81, 229):

Similarly, the metal center can also have a considerable shifting effect.
Consider the following dppm chelates with 4-member rings:
W(CO)4(2-dppm) 23.7 ppm
Mo(CO)4(2-dppm) 0 ppm
Cr(CO)4(2-dppm) 23.5 ppm
 Sabhuku Mudavanhu
Phosphines 19
31P NMR, as with 1H and 13C methods, can be exceptionally useful in
characterizing metal-phosphine complexes and structures:
125 Hz 125 Hz

Ph 2 P PPh 2
OC
Ni
OC
C
O
+23 ppm - 23 ppm

Problem: Which of the following complexes will have the highest

CO stretching frequency in the IR? Why?

A) [Mn(CO)3{P(OPh)3}3]+

B) W(CO)3(PEt3)3

C) [(PF3)Ag(CO)]+

Problem: Which of the following complexes will have the lowest

CO stretching frequency in the IR? Why?

A) Ni(CO)(PMe3)3

B) Fe(CO)4(PPh3)

C) [Re(CO)2{P(OMe)3}4]+
 Sabhuku Mudavanhu
Hydrides 1

Hydride Ligands

bridging mode

{M
M
H anionic 2e donor H H
M
1e to each M

Hydride nomenclature comes from the NMR behavior:

M-H ~ 5 to 25 ppm for d1 d9 metals!!
upfield shift indicates “hydridic” chemical nature

HCo(CO)4 1H NMR = 10.7 ppm

BUT: HCo(CO)4 H+ + Co(CO)4

strong acid in H2O, MeOH
similar to HCl !!

d0 Cp*2ZrH2  = + 7.5 ppm

d10 [HCu{P(p-tolyl)3}]6  = + 3.5 ppm

The presence of partially filled d orbitals on the transition metal has a

considerable shielding effect (moves the chemical shift of the NMR
resonance to more negative ppm) on the hydride 1H NMR chemical shift
position.

IR Spectra: M-H 2200 - 1600 cm1 } can be very weak or absent

M2(-H) 1600 - 800 cm1 } broader (weak or absent)

Late Transition Metals: tend to be more “protic”

Early Transition Metals: tend to be more “hydridic”
(plenty of exceptions; charge on complex important)
 Sabhuku Mudavanhu
Hydrides 2
pKa Values for Transition Metal Hydrides in Various Solvents
Solvent
Metal Hydride Complex H2O MeOH CH3CN
HV(CO)6 strong acid
HV(CO)5(PPh3) 6.8
CpCrH(CO)3 5.4 13.3
CpMoH(CO)3 6.2 13.9
Cp*MoH(CO)3 17.1
CpWH(CO)3 8.0 16.1
CpWH(CO)2(PMe3) 26.6
HMn(CO)5 15.1
HRe(CO)5 ~21
H2Fe(CO)4 4.0 11.4
H2Ru(CO)4 18.7
H2Os(CO)4 15.2 20.8
CpFeH(CO)2 19.4
Cp*FeH(CO)2 26.3
CpRuH(CO)2 20.2
HCo(CO)4 strong acid strong acid 8.4
HCo(CO)3{P(OPh)3} 5.0 11.4
HCo(CO)3(PPh3) 7.0 15.4
HNi[P(OMe)3]4+ 1.5 12.3
HPd[P(OMe)3]4+ 1.0 8.0
HPt[P(OMe)3]4+ 10.2 18.5
H4Ru4(CO)12 11.7
H4Os4(CO)12 12.3
H2Ru4(CO)13 11.1
 Sabhuku Mudavanhu
Hydrides 3

Problem: Which of the following pairs of metal hydrides is the most

acidic (lowest pKa )?

a) HRh(CO)(PEt3)2 -or- HCo(CO)(PPh3)2

b) HMn(CO)5 -or- HRe(CO)5

c) Cp2V(H)(NCMe) -or- [Ru(C6H6)(CO)2(H)]+

d) [HNi(CO)2(dmpe)]+ -or- [HPt(CO)2{P(OMe)3}2]+

e) CpFe(H)(CO)2 -or- CpOs(H)(CO)2

 Sabhuku Mudavanhu
Hydrides 4
Structural Features:
Hydride is the smallest ligand and as a result, M-H distances are typically
quite short: 1.8 to about 1.5 Å, depending on the metal. Periodic trends
are followed, as noted for phosphine-metal distances. Hydrides can be
quite difficult to observe via X-ray diffraction (the most common
technique used to determine structures) due to the very small number of
electrons on the hydride vs. adjacent atoms, especially the metal.
Therefore, neutron diffraction studies are considered best for accurately
locating and identifying hydrides on metal centers.
Synthesis: For moderately electron-rich metals with 2 or more d
electrons, the oxidative addition of molecular H2 to the metal center is
quite common and very important for catalysis:
MLn + H2 H2MLn
H
Ph3P PPh3 Ph3P PPh3
Rh + H2 Rh
Ph3P Cl Ph3P H
Cl
Occasionally, if the metal center has the right amount of electron density
(not too much, not too little) molecular H2 complexes can form:
PMe3 H-H = 0.84 Å
(0.74 Å in free H2) W(H2)(CO)3(PMe3)2
CO H
Note how one writes
OC W First molecular molecular H2 bound to
H H2 metal complex
OC Greg Kubas
a metal.
PMe3 (Los Alamos)

Hydrides can also be formed from the oxidative addition of “active”

hydrogen sources such as silanes (HSiR3) or acids:
RhCl(PMe3)3 + HSiR3 HRhCl(SiR3)(PMe3)2

Os(CO)3(PPh3)2 + HX [HOs(CO)3(PPh3)2](Cl)

Naturally, hydride sources like LiAlH4, borohydrides, or even NaH can be

used to substitute off more weakly coordinated ligands like halides.
 Sabhuku Mudavanhu
Alkyls 1

Alkyl, Aryl, Carbene, Alkylidene & Carbyne Ligands

R
Anionic
M CH3 M C M 2 e- donors
R
R
Alkyls are typically very strong anionic -donors, second only to
hydrides. They have virtually no -acceptor ability.
Increasing the carbon substitution (replacing hydrogens with
hydrocarbon groups, methyl ethyl isopropyl) usually
increases the donor strength, but steric factors can come into play and
weaken the metal-alkyl bond (e.g., t-butyl groups are often too sterically
hindered to bind well).
Replacing the hydrogens with fluorine atoms (very electron
withdrawing) dramatically reduces the donor ability of the alkyl (aryl).
For example, CF3 and C6F5 are not very strong donors.
Metal alkyls are also typically quite to extremely reactive to molecular
O2, water, and a variety of other ligands and reagents. As with hydrides,
they play a very important and active role in catalysis.
-Hydride Elimination
One of the most common
“side” reactions of alkyls is
called the -hydride
elimination reaction:
 Sabhuku Mudavanhu
Alkyls 2

The main driving force for -hydride elimination is the formation of a

stronger M-H bond (almost always stronger than M-alkyl) and the
generation of an alkene ligand that reduces the unsaturation of the metal
complex. The reverse reaction, however, also can occur and is called a
migratory insertion. This is very important in transition metal reaction
chemistry and catalysis, as we will see in later chapters.

Note that in order to have a -hydride elimination you MUST have

a empty orbital on the metal cisoidal (next) to the alkyl ligand. You
also must have -hydrogens present on the alkyl.

In order to prepare stable M-alkyl complexes one, therefore, often needs

to stay away from alkyls with -hydrogens (or avoid metals with empty
coordination sites). Some common ligands used to avoid -hydride
elimination reactions are shown below.
M M M
Me
M CH3 Si Me

Me Me Me Me
methyl neopentyl benzyl trimethylsilylmethyl

Problems:
a) Why doesn’t a 16e- M-phenyl do a -hydride elimination?
H H
Me
M H M
Me

H H Me
b) Would a 16 e- M-(t-butyl) complex be stable or not? Why?
 Sabhuku Mudavanhu
Alkyls 3

-Hydride Elimination
A less common reaction with metal alkyls is the -hydride elimination,
where a hydrogen atom on the -carbon is added to the metal to
generate a M=CR2 (carbene or alkylidene) group and a hydride:
Me Me Me Me Me
Me
H
Me H H Me
-hydride Me migratory
elmination insertion
Cl P Cl
P Cl H
Ta P Ta Ta
P P
Cl
could also
be considered
P Cl
an oxidative
Cl
addition Practice your electron counting!!

Note that just as with a -hydride elimination, it is important to have

an empty orbital cis to the -hydrogen in order to have the -
hydride elimination occur. In the next section on carbene/alkylidene
ligands, we will see that depending on how you electron count, an -
hydride elimination can also be considered to be a C-H bond oxidative
addition (see that chapter as well).
Synthesis:
The most common way of making metal alkyls is to do what is called a
transmetallation, that is react a transition metal halide with a alkali or
main group metal alkyl, which is typically far more ionic and reactive:
M–X + LiR M–R + LiX
Other reactive alkyl reagents: RMgX (Gignard), R2Zn, R2Hg, R2Cu, AlR3

WCl6 + 6AlMe3 WMe6 + 6AlClMe2

Problem: Based on core photoelectron spectroscopy, which complex

is more electron-rich at the metal – W(CH3)6 or W(CO)6 ?? Why?
 Sabhuku Mudavanhu
Alkyls 4
The other common way of making M-alkyls is to react a moderately
electron-rich metal center with an alkyl halide (RCl, RBr or RI):
MLn + RBr R–MLnBr
This, once again, is called an oxidative addition.
CH3
P I P I
Rh + MeI Rh
P CO P CO
I

This will be discussed more fully in the oxidative addition reaction

chapter.
Aryl Ligands
Aryl ligands are relatively strong anionic two
electron donors, essentially just like alkyls. M
Since they cannot easily -hydride eliminate
(formation of the benzyne intermediate is
typically too unstable), metal aryl complexes are usually relatively
stable compared to alkyls with -hydrogens. But “stable” is a relative
term since transition metal aryl complexes are also quite air-sensitive
and reactive.
Aryls do have the potential for both -donation and -backbonding
through the filled aryl -orbitals and empty * antibonding orbitals.
This can provide additional stability to a metal complex, depending on
whether the metal needs additional electrons from the ligand or wants to
dump excess electron density onto the ligand.
Problem: Cp2Re-CH2CH3 is very stable under inert atmosphere,
but Cp2Sc-CH2CH3 readily decomposes. Why?
 Sabhuku Mudavanhu
Alkyls 5

Fischer Carbenes

In 1964 Fischer’s group prepared the first transition

metal carbon double bond, which he called a carbene,
after the very reactive neutral organic CR2 fragment.
O
(OC)5W
CH3
CH3
(CH3)3O+ O
W(CO)6 + CH3Li (OC)5W
CH3
O Ernst O. Fischer
(OC)5W Technical University of Munich,
Germany
CH3

The reaction of Cr(CO)6 with Li[N(i-Pr)2], followed by reaction with

Et3O+ generated the analogous Cr carbene complex with Et and N(i-Pr)2
groups on the carbene. A crystal structure of this complex revealed the
following unusual features of the Cr=C(Et)[N(i-Pr)2] group:
OEt 1.35 Å (normal distance should be
2.13 Å (Cr-R single bond 1.41 Å, a 0.06 Å shortening)
distances are 2.0-2.2 Å) Cr
N(iPr)2 1.33 Å (normal distance should be
1.45 Å, a 0.12 Å shortening)

Thus, the X-ray structure indicated that the actual electronic structure of
this “carbene” was really more like one of these resonance hybrids:

OEt OEt
Cr Cr
N(iPr)2 N(iPr)2

The presence of 5 electron-withdrawing CO ligands would certainly

help “suck up” the formal negative charge that these resonance
structures put on the metal.
 Sabhuku Mudavanhu
Alkyls 6
The bonding description commonly used to describe Fischer Carbenes is
to treat the carbene as a neutral 2e- donor ligand that really only makes a
single bond to the metal (BUT, we often draw it as a double bond!!). In
considering the carbene as a neutral ligand, it has one filled orbital (sp2
hybrid) that donates it’s lone pair to an empty orbital on the metal in a
typical ligand fashion. But it also has one empty orbital (pure p
character) that wants to interact with a lone pair of electrons in order to
form a stabilizing bonding interaction. This is a singlet state carbene
formalism and the possible orbital interactions are shown below:

If the metal is electron deficient (perhaps due to all the good -acceptor
CO ligands) then it can’t -donate very well to the carbene. Thus we
end up with a M-C single bond (even though we draw a double bond!)
and some multiple bond character between the carbene carbon and the
-donor groups attached to it (like a NR2, OR, SR, Ph, etc).
Most Fischer Carbenes have d 6 metal configurations (assuming that we
electron count the carbene ligand as a neutral 2 e- donor), but d 4 and d 8
systems are known.
 Sabhuku Mudavanhu
Alkyls 7
The bond strength in Fischer Carbenes depends on several factors:

Weak M=C Strong M=C

Metal Electron-deficient Electron-rich

(electron withdrawing ligands (electron donating ligands, 3rd
like CO, NO, 1st row metal, row metal)
electronegative metal)

Carbene groups Good donating functional Simple sigma donors like H or

groups that can -bond to the CH3 that can’t -donate to the
carbene (like NR2, SR, OR, Carbene carbon atom.
Ph); more than one donating
group really weakens the M-C
bond!!

Note that most Fischer Carbenes favor the weak bonding situation,
where the metal has a d 6 configuration (counting the carbene as neutral
ligand), CO ligands, and the carbene has -donating groups. The d 6
configuration naturally favors the middle to late transition metals. The
strong carbene bonding situation is actually considerably more reactive,
much like the reactivity of a C=C double bond vs. a C-C single bond.
The C=C double bond is stronger than the single bond, but it is
kinetically considerably more reactive due to its unsaturation.
Problem: Choose the complex that has the stronger M=C bond. Is
there a large or small difference in bond strengths? Explain.
a) [Cp(CO)2(PPh3)Mo=CH2]+ -or- [Cp(CO)2(PPh3)W=CH2]+

b) [Cp(CO)2(PPh3)W=CH2]+ -or- [Cp(CO)2(PEt3)W=CH2]+

c) [Cp(dppe)Fe=CH2]+ -or- [Cp(NO)(PPh3)Re=CH2]+ (tricky!)

 Sabhuku Mudavanhu
Alkyls 8
Problem: Order the following Fischer Carbenes from the weakest
to the strongest M=C bond. Explain.
a) Ph OMe b) Ph Me c) MeO OMe
C C C
H3C O
C O
N P(OMe)3 Me3P PMe3 C C
Re Re Mn
(MeO)3P C Me3P C C C
O O O O
Cl I Cl

The other reactivity characteristic of Fischer Carbenes is that because

the carbene carbon atom formally has an empty p orbital, it is very
susceptible to nucleophillic attacks there. On the other hand,
electrophiles tend to attack the metal center where there are a number of
metal based lone pairs available.

Schrock Alkylidenes

In 1973 Richard Schrock, while working at DuPont

central research, prepared the first early transition
metal complex with a metal=carbon double bond:
(t-butyl-CH2)3TaCl2 + 2Li(CH2-t-butyl)

-elimination H
Ta(CH2-t-butyl)5 (t-butyl-CH2)3 Ta
Richard Schrock
unstable intermediate Me MIT

Me Me

+ neopentane

This turned out to be a key development in early transition metal

chemistry.
 Sabhuku Mudavanhu
Alkyls 9
Unlike most Fischer Carbenes, these early transition metal alkylidene
complexes did have clear-cut and strong metal=carbon double bonds.
For example, the crystal structure of the Cp2Ta(=CH2)(CH3) complex
has the following bond distances:

2.24 Å
CH3
138° Ta The Ta=CH2 bond is distinctly shorter
CH2 than the Ta-CH3 single bond!
2.03 Å

The reason that Schrock gave these “carbene” complexes a different

name (alkylidenes) was not just because of the structural differences.
These early transition metal alkylidene complexes had very different
(almost opposite) reactivities compared to Fischer Carbenes:
Fischer Carbenes Schrock Alkylidenes

Nucleophillic attacks at carbon atom of Electrophillic attacks at carbon atom of

carbene (carbon is electron deficient) alkylidene (carbon is electron-rich)

Electrophillic attacks on metal center Nucleophillic attacks on metal center

(metal is more electron-rich, often d6 18 (metal is electron-deficient, usually d2 or
e- system) d0 16 or 14 e- count)

Carbene is stabilized by heteroatom Alkylidene is destabilized by heteroatom

groups that can -bond to it. Likes NR2, groups that can -bond to it. Strongly
SR, OR, or Ph groups. prefers H or simple alkyl groups.

Later transition metals favored, Early transition metals favored,

especially with d6 counts (carbene as especially with d0 centers (alkylidene as
neutral 2e- donor ligand) dianionic 4e- donor)
 Sabhuku Mudavanhu
Alkyls 10
The bonding description commonly used to describe Schrock
Alkylidenes is to treat the alkylidene as a dianionic 4e- donor ligand,
which is what the electron
counting and valence rules from
the first chapter would indicate.
The filled p-orbital on the
alkylidene carbon nicely
explains the tendency for
electrophiles to attack at this
site, while in a Fischer carbene
this same orbital is formally
empty and thus susceptible to a
nucleophillic attack.
Similarly, the d0 metal center in the typical Schrock alkylidene usually
only has a 12 to 16 e- count (often 14 e-), this means that there are
several empty low energy orbitals that are very attractive to any
nucleophile that can sterically access the metal center. In Fischer
carbenes, the metal is typically d6 and 18e-, thus there are no empty
orbitals on the metal for a nucleophile to attack.
One other way to view a Schrock alkylidene is as a neutral ligand, just
as with a Fischer carbene, but that it is in the triplet carbene state and
interacting with a spin unpaired d2 metal
center:
The view of an alkylidene as a neutral
triplet carbene forming a strong covalent
double bond to a triplet metal center is
very analogous to the covalent C=C
double bond in organic chemistry.
 Sabhuku Mudavanhu
Alkyls 11
Molecular orbital (MO) diagrams for generic Schrock alkylidene and
Fischer carbene ligands are shown below starting with both carbon
fragments as neutral triplet (alkylidene) and singlet (carbene) groups:



alkylidene 
metal d empty d p and sp2 
orbitals orbitals orbitals p

metal d carbene
orbitals

sp 2

 this extra d
orbital used for

 bonding to
other ligands


Schrock alkylidene Fischer carbene
2
Metal = d Metal = d6
alkylidene triplet state carbene singlet state
(Ta 3+, Nb 3+, etc) (Cr0, Mo 0, Re +1, etc)

Note that the higher energy early transition metal orbitals match up
much better with the higher energy triplet alkylidene orbitals – this leads
to considerably stronger covalent bonding (both MO diagrams are on the
same energy scale).
 Sabhuku Mudavanhu
Alkyls 12
So How Should I Electron Count??
The various methods of electron-counting carbenes and alkylidenes are:
1) both as neutral 2 e- donor ligands (but still draw a M=C double bond)
2) both as dianionic 4 e- donor ligands
3) Fischer carbenes as neutral 2 e- donor ligands. Typically group 6 or
higher metals with a d6 or d8 electron count (sometimes d4).
4) Schrock alkylidenes as dianionic 4 e- donor ligands. Typically group 4
or 5 metals with d0 electron counts. Also later transition metals in high
oxidation states (d0, d2, or d4).
Of course, in order to do method 3 or 4, you have to realize whether you have a
Fischer or Schrock system. This isn’t always easy just looking at the complex. I
recommend uniformly adopting methods 1 or 2.
It is somewhat important to be able to tell them apart since Schrock alkylidenes
almost always have stronger (but often still very reactive) M=C bonds compared
to Fischer carbenes. So on a question asking you to order a series of carbene
and/or alkylidene complexes, it is generally important to figure out which is
which. On this type of question I’ll only give you a maximum of one Schrock
alkylidene since the factors determining alkylidene bond strengths are not
anywhere as clear cut as those for Fischer carbenes. On assignments, I will also
generally give you clear cut examples.

As far as the overall electron-count is concerned, it DOESN’T

matter which electron-counting method you use, since both give you
the same overall electron-count!!
Example: Identify the following complexes as Fischer carbene or
Schrock neutral carbene neutral carbene
2
alkylidene. Ta(+3)
2 Cp
d
12 e- 
Re(+1)
Cp
d
6 e- 
6

Cl Cl 2 e- 2CO 4 e-
Ta CH2 2 e-
OC
Re C(OR)H 2 e-
CH2
18 e-
OC RO 18 e-

d2 early TM using neutral d6 mid-TM using neutral

carbene indicates a Schrock carbene indicates a Fisher
alkylidene complex carbene complex
 Sabhuku Mudavanhu
Alkyls 13
NMR Data
There isn’t any clear cut way of distinguishing Fischer carbenes from
Schrock alkylidenes. Some complexes, of course, will fall in between
either category (shades of gray) and can’t be clearly identified.
13C NMR data is potentially one way of distinguishing between
carbenes and alkylidenes because the chemical shift of the carbene
carbon is usually quite sensitive to 13C
the chemical environment, Compound  (ppm) Class
electron density, and bonding Cp2Ta(=CH2)(Me) 224 Schrock
factors. Unfortunately, the NMR
(t-BuCH2)3Ta(=CH(t-Bu) 250 Schrock
data, although sometimes useful,
generally won’t allow one to (OC)5Cr(=CH(NMe2)) 246 Fischer

identify when a system is a (OC)5Cr(=CPh(OMe)) 351 Fischer

carbene or alkylidene, as shown in (OC)5Cr(=CPh2) 399 Fischer
the table to the right.
1H NMR data has provided useful information about carbene rotational
barriers. As with most double bonds, there is a rotational barrier for the
M=CR2 bond. For Schrock alkylidenes this is usually quite high (G‡
> 100 kJ/mol), but for the more weakly bonded Fischer carbenes this can
often be readily determined from variable temperature 1H NMR studies.
The Cr carbene shown below actually has more double bond character
between the carbene carbon and the -OMe group relative to the Cr=C
bond. At 25ºC the methoxy CH3 group shows a single 1H NMR
resonance indicating that there is relatively fast rotation about the C-
OMe bond, while at 40ºC
H3C
there are two resonances
O O CH
for the methoxy CH3 (OC)5 Cr (OC)5 Cr
3

group, one for the cis and

CH3 CH3
trans conformers,
consistent with partial trans cis
double bond character.
 Sabhuku Mudavanhu
Alkyls 14
The Hot Carbene Ligand
The hottest “new” ligands are imidazole-based N-heterocyclic carbenes
(NHC’s) shown below. The flanking N atoms and R groups provides
steric and electronic stabilization making this a reactive, but
synthetically accessible ligand. R
NHC’s are usually strong -donors, N
often exceeding the donor ability of M
N N
an alkylated PR3 ligand (see plot R R
N
below). The backbone double bond
R
may or may not be present (along
with other R groups).
PPh3
2070
Tolman Electronic Parameter (cm -1)

Ph
Note that this ligand is P(p-tol)3
PMe2Ph
usually drawn with a Pr
N N Me
PiPr3
PMe 2Ph
i

single bond to the metal. 2060 PEt3

Ph
Crabtree's abnormal NHC
But it is NOT an anionic PCy3
alkyl and there is NOT a 2050
H atom on the carbon N N
Ph Ph
Bu Bu

atom bound to the metal

2040 N N R 2 = 0.91
center!! It is typically Pri Me

electron-counted as a
2000 2010 2020 2030 2040 2050
neutral Fischer carbene. -1
avg(CO) for Ir(CO)2Cl(L) (cm )
Because of the two
flanking N atoms that can -donate into the empty carbene p-orbital, it is
not considered to be a good -acceptor. This -donation, however, does
help make it a stronger -donor by compensating for the -withdrawing
electronegative N atoms.
Some References to N-heterocyclic carbenes:
Wolfgang A. Herrmann, “N-Heterocyclic Carbenes. Part 31. N-Heterocyclic Carbenes: A New Concept in
Organometallic Catalysis.” Angew. Chem. Int. Ed., 2002, 41, 1290-1309.
Robert H. Crabtree (& coworkers), “Abnormal C5-Bound N-Heterocyclic Carbenes: Extremely Strong
Electron Donor Ligands and Their Iridium(I) and Iridium(III) Complexes.” Organometallics, 2004, 23,
2461-2468 (modified CO plot above from this reference).
 Sabhuku Mudavanhu
Alkyls 15
Problem: Order the following M=C complexes from the one with
the highest M=CR2 rotational barrier to the lowest. What factors
affect the M=C rotational barrier? Identify each complex as either
a Fisher carbene or a Schrock alkylidene.

a) H Me b) Ph Me
C C
H 3C CH3 Me3P PMe3
Os Fe
H 3C O Me3P Br
CH3 Br

c) Me2N NMe2 d) Ph OMe

C C
O C O O
C C P(OMe)3
Ru Fe
C Cl (MeO)3P Cl
O
Cl Cl
 Sabhuku Mudavanhu
Alkyls 16

Carbynes/Alkylidynes M C R

E. O. Fischer accidentally prepared the first M≡C-R triple bonded

compound in 1973:
MeO R planned rxn X R
didn't work
CO
CO
OC M CO
OC M CO + BX3 OC
OC CO
OC R
C
CO
M = Cr, Mo, W
X = Cl, Br, I OC M CO
R = Me, Et, Ph OC
X

He called this a carbyne after alkyne, which refers to a C≡C triple bond.
Early transition metal versions were prepared first by Schrock in 1978
via -deprotonation of the alkylidene:

1. PMe3
Ta Ta + [Ph3PCH3]Cl
Cl H Cl
2. Ph3P=CH2 C
Cl Me3P R
R

These were called alkylidynes by Schrock. Fortunately, while there are

some differences between early and later transition metal carbon triple
bonds, we can treat them as basically being the same. Thus, one can
simply treat carbynes and alkylidynes as trianionic (-3) 6e- donating
ligands. They are very strong donors as might be expected from the
relatively low electronegativity of carbon and the -3 formal charge.
Ph
Ph H
C
CO CO
CO = 1938 cm-1 CO = 1870 cm-1
Cl W PMe3 Cl W PMe3
Me3P Me3P
Cl Py
 Sabhuku Mudavanhu
Alkyls 17
An remarkable X-ray structure of one of Schrock’s compounds that
contains a W-C single bond, a W=C double bond, and a W≡C triple
bond is shown below and beautifully illustrates the dramatic and
progressive shortening of the W-C bonds as you increase the bond order:
Ph 2.25Å
1.78Å
C CMe3

P CH2
W
C H 1.94Å
P
Me3C
Carbynes are also rather good bridging groups for two or three metal
centers. When bridging two metals, one usually assumes delocalized
bonding and that the carbyne donates 3e- to each metal center:

R R 1.94Å
O O
C C OR C C OR

RO Re Re OR RO Re Re OR
RO C C RO C C
O O
R 2.69Å R
Schrock, JOMC, 1996

X-ray structures (as the one above) usually show equal M-(-carbyne)
bond distances completely supporting the idea that the bonding is
delocalized. When there isn’t M-M bonding present, most authors will
draw a circle in the dimetallocyclobutane ring to indicate delocalized
bonding (that doesn’t necessarily mean it is aromatic, but it may be
depending on the - and d-electron count).
 Sabhuku Mudavanhu
Alkyls 18

Problem: Which of the following ligands will coordinate the

strongest to the empty coordination site on the metal complex shown
below.
CO, PMe3, P(OMe)3, CH3, F, CF3

Mn(CO)5+

Problem: Professor Standshort instructed his graduate student

Fred Fasthands to make a Pd(alkyl)2(PPh3)2 complex. Fred
immediately rushed into the lab and ran the following reaction:

PdCl2 + 2PMe3 + 2EtMgBr icky black stuff + ethylene (g)

Thelma Thinksalot, a younger yet wiser undergraduate in the lab

(who was taking Prof. Standshort’s organmoetallics class), noticed
this and suggested that Fred use the exact same conditions except
that he should use PhCH2MgBr (benzyl Grignard) instead of
EtMgBr. Fred frantically did so and found that the reaction now
gave a quantitative yield of orange Pd(CH2Ph)2(PMe3)2.
Why didn't the first reaction work and why did the second work
fine? What other alkyl groups might work?
 Sabhuku Mudavanhu
Alkenes & Alkynes 1

Alkenes & Alkynes

Alkenes act as neutral 2e- donors (per C=C double bond). Due to the
presence of empty * antibonding orbitals, there is the possibility of
some -backbonding:

C C Dewar-Chatt-
M M Duncanson
bonding
C C model (1953)

-donation via the -back donation via the

filled alkene -system empty alkene -system

Alkenes are typically relatively weakly coordinating ligands. They are

also extremely important substrates for catalytic reactions. The strongest
alkene-metal bonds occur with third row metals (as with almost all
ligands) and when one can get more -backbonding to occur. The
amount of -backbonding depends strongly on how electron-rich the
metal center is and whether or not there are electron-withdrawing groups
on the alkene to make it a better acceptor ligand.
NC
H H H H
NC
Cl
PR3 PR3
Pt Cl Pt Pt
Cl PR3 PR3
H H H NC
H
NC

Pt(2+) Pt(0) Pt(+2)

C=C = 1.37Å C=C = 1.43Å C--C = 1.49Å
Zeiss's Salt metallocyclopropane

In extreme cases, as shown above to the right, if the metal is electron-rich

enough and if there are electron-withdrawing groups on the alkene (like
the CN’s), one can actually get a formal oxidation of the metal via the
transfer of 2e- to the alkene to form a dianionic metallocyclopropane
ligand that is now coordinated via two anionic alkyl -bonds (thus the
assignment of Pt(+2)).
 Sabhuku Mudavanhu
Alkenes & Alkynes 2

Another interesting comparison is F C=C = 1.40Å

shown to the right where we have two F Rh-C = 2.02Å
different alkenes coordinating to the
F
same metal center. The electron- F
withdrawing fluorine groups on the Rh
F2C=CF2 alkene makes it a better - H
H
acceptor ligand. This weakens the
H C=C = 1.35Å
C=C bond, but strengthens the alkene- H Rh-C = 2.16Å
metal bond.

Another series of structures is shown below for butadiene, Fe(4-

C4H6)(CO)3, and Cp2Zr(4-C4H6):
1.46Å
1.45Å 1.46Å
1.40Å

Fe
Zr
1.36Å C C 1.45Å
O C O
O

In this series one can see that the combination of -backdonation from
the Fe and -donation from the alkenes to the Fe weaken and lengthen
the C=C bond. In the Zr complex, however, we see an interesting
reversal where the single bond across the back of the butadiene shortens
quite a bit. What is happening here is that the Zr is in a very low
oxidation state (+2, but it really wants to be +4) and
is, therefore, extremely electron-rich. So electron-rich
that it transfers two electrons to the butadiene via the Zr
-backdonation and generates a metallocyclopentene
resonance structure, shown schematically to the right.
 Sabhuku Mudavanhu
Alkenes & Alkynes 3
More Electronic Effects
Electronic effects with alkenes can often be somewhat easily monitored
using infrared (IR) spectroscopy, much as with CO ligands. The more -
backbonding, the weaker the C=C double bond and the lower the C=C
stretching frequency in the IR. The table below shows a series of alkene
compounds with differing amounts of -
C=C
donation and -backbonding. Note that Ethylene Complex (cm1)
both weaken the C=C bond and lower the Free Ethylene 1623
stretching frequency, although the - [Ag(H2C=CH2)2]+ 1584
backbonding has by far the larger effect. Fe(CO)4(H2C=CH2) 1551
[Re(CO)4(H2C=CH2)2]+ 1539
The Ag+ complex is believed to have no [CpFe(CO)2(H2C=CH2)]+ 1527
-backbonding, so the drop in the C=C Pd2Cl4(H2C=CH2)2 1525
stretching frequency is completely due to [PtCl3(H2C=CH2)] 1516
-donation from the alkene to the Ag+. CpMn(CO)2(H2C=CH2) 1508
Pt2Cl4(H2C=CH2)2 1506
Carefully examine the compounds in the
CpRh(H2C=CH2)2 1493
table and see if the changes in the C=C
stretching frequencies make sense
relative to your perceptions of how electron-rich the metal center is
(allowing you to judge the amount of -backdonation) and how strongly
the alkene might be -bonding to the metal (a relatively minor
contribution compared to the effect of -backdonation).
The thermodynamic stability of metal-alkene complexes is strongly
affected by the nature of the alkene (and metal):
1) Electron-withdrawing groups on the alkene generally increase the strength
of the metal-alkene bonding, while electron-donating groups generally
decrease the stability.
2) In cases where cis-trans isomerism is possible, the more stable complex is
almost always formed by the cis-alkene (steric factors).
 Sabhuku Mudavanhu
Alkenes & Alkynes 4

3) Metal complexes of ring-strained cycloalkenes (e.g., cyclopropene) display

higher than expected stability. The ring strain raised the energy of the
cycloalkene ring system making it a better donor to the metal center (better
orbital energy matching). See the next section on cyclobutadiene for a
particularly remarkable example.

4) Chelating dienes show the expected stabilization from the chelate effect.
The most common examples are norbornadiene and cyclooctadiene shown
below. Note that these can still be easily substituted off the metal by
stronger coordinating ligands such as phosphines.

M
M
norbornadiene cyclooctadiene
complex complex

5) Third-row metals form the strongest bonds and most stable complexes (as
with most ligands).

Problem: To which of the following (each with a single open

coordination site) will trifluoroethylene bond to the most strongly?
Why?
a) b) ?
? Me2
OC CO P CO
Cr W
OC CO P PMe2
Me2
CO Me2P

c)
O
F F
Ti
? F H
 Sabhuku Mudavanhu
Alkenes & Alkynes 5
Cyclobutadiene
Cyclic conjugated -systems are aromatic if the number of -electrons
equals 4n + 2 (where n = an integer). Cyclobutadiene is an anti-aromatic
since it has 4 -electrons. The anti-aromaticity combined with the ring
strain makes this simple molecule too unstable to exist as a free organic
compound.
A triumph of the early days of organometallic chemistry was the
successful synthesis of (4-C4H4)2Ni2(-Cl)2Cl2, a stable metal-
coordinated butadiene molecule, by Criegee in 1959. This was actually
predicted theoretically by Longuet-Higgins and Orgel in 1956 using an
early form of molecular orbital theory.
Me
Me Me Me

Cl Me Cl Me
+ Ni(CO)4 Ni
Cl
Ni
Cl
Cl
Me Me Me Cl Me
Me Me

An even simpler route was discovered shortly after this involving the
cyclodimerization of diphenyl acetylene by Fe(CO)5:
O
O
CO
C
C
2 Ph Ph + Fe(CO)5 Fe
Ph Ph

Ph Ph

The high stability of a cyclobutadiene coordinated to a metal arises from

the mixing of the 4  electrons on the cyclobutadiene with one of the
metal d orbitals that has 2 e- and the right symmetry to mix in and form a
6  electron aromatic system! This is shown on the MO diagram on the
next page. Note that the high energy (instability) of the non-bonding
cyclobutadiene highest occupied molecular orbital (HOMO) allows it to
interact extremely well with the metal orbitals that are at approximately
the same energy.
 Sabhuku Mudavanhu
Alkenes & Alkynes 6



Fe

Fe Fe

metal d
orbitals non-bonding
Fe
cyclobutadiene
, non-bonding,
and * orbitals

Fe Fe
 Fe


Fe

Fe
Alkynes
Alkynes are essentially like alkenes, only with another perpendicular pair
of -electrons. Thus they can act as neutral 2 or 4 e- donors, depending
on the needs of the metal center. They are also much better bridging
ligands because of this second set of -electrons.
Note how the bridging alkyne is drawn. This indicates a
R C C R
R
C C R perpendicular bridging mode and that both carbons are
interacting equally with both metals (the alkyne is donating
2e- to each metal). It dos NOT indicate that each carbon
M M M has 6 bonds to it !!

Alkynes are better donors compared to alkenes and typically coordinate

far more readily to a metal for steric (more open, less hindered) and
electronic (better donor, 2 or 4e- bonding) reasons. They are also quite a
 Sabhuku Mudavanhu
Alkenes & Alkynes 7
bit more reactive for doing C-C coupling (see the Fe mediated cyclo-
dimerization example for making the substituted metal-bound butadiene
on the previous page) and other reactions.
When alkynes bridge, they almost always do so perpendicular to the M-
M axis, the parallel bridging mode is known, but quite rare:

Cp2Rh2[-(CF3C≡CCF3)](CO)(CNR) Co2[-(HC≡CH)](CO)4(PMe3)2

Alkynes also have a strong tendency to bridge more than two metals in
cluster compounds.

Problem: The Cp2Rh2[-(CF3C≡CCF3)](CO)(CNR) complex shown

above has a Rh-Rh bond distance of 2.67 Å, strongly indicating a
covalent bond between the rhodium atoms. How would you electron
count this complex to accommodate a Rh-Rh covalent bond?
 Sabhuku Mudavanhu
Alkenes & Alkynes 8
Problem: Which of the following ligands will coordinate the most
strongly to a generic metal center (not too electron-rich or deficient,
with enough open coordination sites)?

a) b)

c) d)
 Sabhuku Mudavanhu
Arenes 1

Arenes
Arenes (benzene being the simplest member of this family) typically
coordinate in an 6 fashion and as such are neutral 6 e- donors, although
they can adopt lower coordination modes (4 and 2).

6 M M 4
Synthesis: The first metal-benzene complex was prepared in 1955 by
Fischer and Hafner:
1. AlCl3 1. Na2S2O4
3CrCl3 + 2Al + 6C6H6 3[Cr(6-C6H6)2]+ Cr(6-C6H6)2
2. H2O 2. KOH
Limitations: Low yield, messy, difficult to isolate organometallic product. Also the
arene must be inert towards the very reactive AlCl3. Alkylated arenes are isomerized
by AlCl3. Arenes with substituents that have lone pairs available (e.g., haloarenes,
anilines, phenols, etc.) are also unsuitable since they can bind to the AlCl3 and inhibit
the reaction.

Metal-atom vapor synthesis was first used by Timms in 1969 to prepare

Cr(C6H6)2. This involved the evaporation of elemental metals under high
vacuum by heating them to very high temperatures (either resistively or
by electron-beam impact). The evaporated metal atoms were condensed
into a layer of frozen ligand and solvent (sometimes the same) coating
the inside of a glass reaction flask at liquid nitrogen temperatures.
Warming the flask up to the melting point of the solvent allowed the
atomic metal and ligands to directly react to make the metal-ligand
complex. Malcom Green, Ken Kabunde, and Philip Skell were all
researchers actively involved in this area in the 70’s.
Limitation: Metal atom vapor reactor is very expensive and difficult to maintain.
 Sabhuku Mudavanhu
Arenes 2
Some Properties of Metal-bis(arene) Complexes
Complex Color mp/ºC Miscellaneous
Ti(C6H6)2 red - air-sensitive, autocatalytic decomposition in
aromatic solvents
V(C6H6)2 red 227 very air-sensitive, paramagnetic, reducible to
[V(C6H6)2]
V(C6H5F)2 red - air-sensitive
Nb(C6H6)2 purple - very air-sensitive, paramagnetic, decomposes at
ca. 90'C
Cr(C6H6)2 brown 284 air-sensitive, the cation [Cr(C6H6)2]+ is air-stable.
Eº = 0.69 V in DME against SCE
Mo(C6H6)2 green 115 very air-sensitive
W(C6H6)2 yellow-green 160 less air-sensitive than Mo(C6H6)
[Mn(C6Me6)2]+ pale pink - diamagnetic
[Fe(C6Me6)2]2+ orange - reducible to [Fe(C6Me6)2]+, violet, and to
Fe(C6Me6)2, black, paramagnetic, extremely
air-sensitive
[Ru(C6Me6)2]2+ colorless - air-stable, diamagnetic; reducible to Ru(C6Me6)2,
orange, diamagnetic, very air-sensitive
[Co(C6Me6)2]+ yellow - Paramagnetic; reducible to Co(C6Me6)2, very
air-sensitive
Adapted from Elschenbroich & Salzer, “Organometallics”, VCH, 1989

-Backbonding
An interesting aspect of metal-arene complexes is that -backdonation
plays a relatively important role in the bonding and chemistry. Arenes
often do not coordinate very strongly to metals, but as one can tell from
the list above, they do tend to favor metals in low oxidation states and
often generate surprisingly stable complexes. Cr(C6H6)2, for example, is
kinetically inert to most substitution reactions, no doubt due to its 18 e-
configuration, but also due to the mix of -bonding and backbonding.
But remember that CO and NO+ are far, far stronger -backbonding
ligands.
 Sabhuku Mudavanhu
Arenes 3
Structural Features
The parallel sandwich structures have the following features:
Distances (Å)
M M-C Ar…Ar C-C
Benzene -- -- 1.39
Ti 2.22 3.48 1.38
Nb 2.33 3.72 1.41
M-C Ar···Ar Cr 2.14 3.21 1.42
M [Cr]+ 2.10 3.20 1.36
Me6-[Fe]2+ 2.14 3.26 1.38
C-C Me6-[Ru]2+ 2.25 3.50 1.40
[Ru]2+ 2.22 3.42 1.42

Note that the C-C bond distances in the arene are not a particularly
reliable gage of the amount of -backbonding, which in turn indicates
that there probably is not a large amount occurring. The decrease in ring
separation in going from [Ru(C6H6)2]2+ to the hexamethylbenzene
complex, [Ru(C6Me6)2]2+ is caused by the increased electron density on
the hexamethylbenzene that makes it more electron-rich and a better
donor group (although that doesn’t always lead to bond shortening). The
Cr-C shortening in the cationic complex probably results from the
contraction of the Cr d orbitals due to the localized positive charge.

Problem: The crystal structure of

[Cr(C6H6)2]+ on the right clearly shows
that the hydrogen atoms on the benzene
distinctly lean in towards the metal
center. Explain why.
 Sabhuku Mudavanhu
Arenes 4

A dramatic example of the “power” of the 18e- electronic configuration

is seen for the [Ru(C6Me6)2]2+ complex. This can be reduced to neutral
Ru(C6Me6)2, but electron-counting with two 6-C6Me6 ligands gives you
a 20e- complex. Violations of the 20e- rule are most common for first
row metals where the metal-ligand bonding interactions are weaker
leading to less destabilization when one occupies an M-L antibonding
orbital when going past 18e-. But for 2nd and 3rd row metals that have
increasingly stronger metal-ligand bonding, going past 18e- costs
considerably more from a stability viewpoint.
Me Me

Indeed, the structure of Ru(C6Me6)2 (shown to Me Me 6

the right) reveals that one of the arene rings is Me Me

strongly folded to give a 4e- 4-coordination Ru

Me Me
geometry. Thus, the correct formulation of this
4
compound is Ru(4-C6Me6)(6-C6Me6), which Me Me

does give an 18e- count. Me

Problem: In which of the following complexes should the 6-benzene

ligand coordinate the strongest?
A) B)

Mo Cr
OC (MeO)3P
CO P(OMe)3
OC (MeO)3P

C)

W
Me3P PMe3
Me3P
 Sabhuku Mudavanhu
Cp 1

Cyclopentadienyl - Cp

The cyclopentadienyl ligand is one of the most common and popular

ligands in organometallic chemistry.
H3C CH3
6e- 6e- stronger donor
strong bulky ligand
donor H3C CH3

CH3

Cp Cp*
It is an anionic ligand that normally coordinates in an 5 mode as a 6e-
donor, but it can adopt 3- and 1-coordination modes.

M
M M

5 3 1
Free neutral cyclopentadiene, which is deprotonated with a strong base
to generate the Cp, is unstable and reacts with itself via a Diels-Alder
reaction to make the dicyclopentadiene. One typically regenerates
cyclopentadiene by distilling (“cracking”) it from the high boiling dimer
solution and storing it in a refrigerator, but it slowly re-dimerizes to
make dicyclopentadiene.

+
 Sabhuku Mudavanhu
Cp 2
Brief History of Ferrocene:

1901 Synthesis of KC5H5 from K and C5H6

1951 Miller, Tebboth & Tremaine
Sythesis of Fe(C5H5)2 from the reaction of C5H6 with freshly
reduced Fe at 300ºC
1951 Kealy & Pauson
3C5H5MgBr + FeCl3 Cp2Fe + + 3MgBrCl
They were trying to make fulvalene!
They proposed that they had made: Fe

1952 E. O. Fischer proposes a “Double-cone structure”

X-ray structural data
Diamagnetism
Chemical behavior

1952 Geoffrey Wilkinson & Robert Woodward: “Sandwich Structure”

IR spectroscopy
Diamagnetism
Dipole moment = 0
Woodward noted that the Cp rings were susceptible
towards electrophillic substitutions, similar to the aromatic behavior of
benzene.
Thus the common name: ferrocene
1973 Fischer & Wilkinson receive the Nobel Prize in Chemistry for
their “discovery” of ferrocene, which played a key role in
opening up the new area of organometallic chemistry.

For a short historical account see Chemical & Engineering News, Dec 3, 2001 (I have copies
of the article) or the special Ferrocene issue of Journal of Organometallic Chemistry, Vol
637-639, Issue 1, 3 December 2001.
 Sabhuku Mudavanhu
Cp 3
The structure of ferrocene does have a sandwich structure with a
bonding interaction from each ring carbon to the metal, although
virtually all researchers only draw a single bond from the metal to the
middle of the Cp ring(s) as shown below in the structural diagram.

Fe

Some Properties of Metallocenes

Complex Color mp/ºC Miscellaneous
“Ti(C5H5)2” green 200 bimetallic with two m-H bridges and a fulvalene
(decomp.) bridging ligand (structure shown later)
V(C5H5)2 purple 167 very air-sensitive, paramagnetic
“Nb(C5H5)2” yellow - bimetallic with 1,5-C5H4 bridges and terminal
hydrides (structure shown later).
Cr(C5H5)2 scarlet 173 very air-sensitive
“Mo(C5H5)2” Black - several bimetallic isomers with fulvalene and h1,h5
bridges and terminal hydrides (structures shown
later), diamagnetic, air-sensitive.
“W(C5H5)2” yellow-green - same as Mo
Mn(C5H5)2 brown 173 air-sensitive and easily hydrolyzed, interesting
high-spin to low-spin interconversion
Fe(C5H5)2 orange 173 air-stable, can be oxidized to blue-green
[Fe(C5H5)2]+ which, in turn, is a good “inert”
oxidizing agent.
Co(C5H5)2 purple-black 174 air-sensitive, paramagnetic 19e- complex, can be
oxidized to the air-stable 18e- yellow [Co(C5H5)2]+
Ni(C5H5)2 green 173 20e- complex, slow oxidation in air to the labile,
orange cation [Ni(C5H5)2]+
Adapted from Elschenbroich & Salzer, “Organometallics”, VCH, 1989
 Sabhuku Mudavanhu
Cp 4
Structural Features
The parallel sandwich structures have the following structural features:
Distances (Å)
M M-C Cp…Cp C-C
Fe 2.04 3.29 1.42
[Fe]+ 2.07 3.40 1.40
M-C Cp···Cp Ru 2.19 3.64 1.43
M
Os 2.19 3.61 1.45
Co 2.10 3.44 1.41

C-C [Co]+ 2.03 3.24 1.42

Ni 2.18 3.63 1.41

Note the various trends in the bond distances. The changes in the
neutral Fe, Co, Ni metallocenes are a direct result of going from 18e-
(Fe) to 19e- (Co) to 20e- (Ni) counts. The extra electrons for the Co and
Ni complexes are going into M-Cp antibonding orbitals, which are
delocalized and progressively weaken the M-Cp bonding, leading to the
increase in bond distances. This in spite of the fact that the metal’s
covalent radius is decreasing as one goes from Fe Ni (effective
atomic number contraction effect).
Problem: Explain why the Fe-C distance lengthens for [Cp2Fe]+,
while the Co-C distance shortens for [Cp2Co]+.

Oxidation of Cp2Os does not produce a simple cationic monomer as

seen for Co and Fe. Instead one
gets dimerization to produce the
following bimetallic complex that
has an Os-Os bond (3.04 Å).
Problem: Is this complex para-
or diamagnetic?
 Sabhuku Mudavanhu
Cp 5
The simple neutral bis-Cp complexes of the early transition metals are
quite different because they are in very low +2 oxidation states (very
electron-rich) and quite unsaturated. Thus, they are very reactive
towards oxidative addition and other reactions.
“Nb(C5H5)2”, for example, is nominally a 15 e- complex with a highly
reactive d3 Nb electronic configuration.
Two molecules of niobocene react with
one another via C-H bond activation H
(oxidative addition) to produce the
Nb Nb
structure shown to the right. Note that
two of the Cp rings are dianionic H
forming both a traditional aninic  6e-
5
-type donor to one metal, while
bridging over and acting as an anionic 2e- -donor to the other metal
center. Practice your electron counting on this.
“Ti(C5H5)2”, is nominally a 14 e- complex with a highly reactive d2
electronic configuration. Two molecules of titanocene also react with
one another via C-H bond activation (oxidative addition) to produce a
bimetallic complex that may well look just like the niobium complex
just discussed. But it has a further reaction (perhaps due to steric
crowding brought on by the smaller Ti centers) leading to the coupling
of the two -bound Cp’s to produce C-C bound bis-Cp and the complex
shown below. The more sterically crowded pentamethyl-Cp (Cp*)
complex simply does a hydride abstraction and stops at the complex also
shown below.
Me Me Me
Me Me
CH2
Me Me Me
H Me
Ti Ti Ti Ti
Me H
Me
H Me Me Me
Me

Me Me
Me Me
Ti-Ti = 2.99 Å
 Sabhuku Mudavanhu
Cp 6
Problem: Electron-count the bimetallic Ti complex to the above
left. Should it have a Ti-Ti bond or not? Show your electron
counting.

Problem: What advantage does the Cp*2Ti complex (above middle)

gain by doing a hydride abstraction to produce the hydride complex
to the above right (previous page)?

The “Mo(C5H5)2” and “W(C5H5)2” complexes might appear to have a

“reasonable” 16 e- count, but they are quite reactive, like their early
transition metal cousins, and also self react with one another via C-H
bond activations to produce several isomeric bimetallic complexes
shown below.

Mo-Mo = 3.19Å

Mo Mo

H THF

50°C
H
H2O 100°C Mo Mo
H
h
H Mo-Mo = 3.36Å
toluene
Mo Mo 70°C

H
 Sabhuku Mudavanhu
Cp 7
Problem: Electron-count the following complex. What does the
arrow between the two Mo atoms indicates? It is NOT a covalent
Mo-Mo bond. What name for this type of bonding would you use?

Mo-Mo = 3.19Å

Mo Mo

Cp Variants
these have special bonding properties important
in substitution reactions (see that chapter)

2-

fulvalenediyl (2-) indenyl (-) fluorenyl (-)

6e-
donor
Mo 2.45Å

azulene

Behrens, Angew. Chem., 1987

Azulene is neutral, so 5-coordination of the C5 ring only provides 5e-,

to get 6e- one needs to use one of the C7 ring carbon -orbitals!
 Sabhuku Mudavanhu
Cp 8
MO Comparison of Cp vs. Arene Ligands

Benzene-Metal Cyclopentadienyl-Metal
Complex Complex

 


metal d metal d
orbitals orbitals







M M
 Sabhuku Mudavanhu
Metal-Metal Bonding 1

Metal-Metal Bonding
There are three general classes of M-M bonding:
Covalent: Electron precise bonds. M-M bond counts as one e-
from each metal center. Most common type of M-M
bonding.
Dative: Where one metal uses a filled d orbital “lone pair” to
coordinate to an empty orbital on a second, more
unsaturated metal. Most dative bonding situations
can also be electron-counted as covalent bonds.
Symmetry: Weak metal-metal interactions caused by molecular
orbital symmetry interactions of filled & empty M-M
bonding and/or antibonding orbitals. Typically seen
for d8 metals. Not at all common.

Overlap of d orbitals to make different types of covalent M-M bonding

interactions (strongest to weakest):
dz 2 

dyz


dxz

dxy 
the dx2- y2 orbitals (not shown) are used for M-L bonding
 Sabhuku Mudavanhu
Metal-Metal Bonding 2
A qualitative MO diagram for the interaction of two square planar metal
centers showing the M-M bond forming interactions:

L M
L
L 
L
L
L
M
L
L  M-M antibonding
orbitals

dz2 dyz dxy

 dxy dyz dz2
dxz  dxz

the dx2-y2, s and px,y

 M-M bonding
orbitals are not shown orbitals
since they are used


for M-ligand bonding

As one fills the lower energy M-M bonding orbitals, one makes one M-
M bond for each pair of electrons added (one per metal). But once you
add more than 8 e- the antibonding orbitals begin to fill and this starts
canceling out M-M bonds.
Electron Count Resulting M-M Bond
d1 - d1 Single bond
d2 - d2 Double bond
d3 - d3 Triple bond
d4 - d4 Quadruple bond optimum
d5 - d5 Triple bond
d6 - d6 Double bond (M-L bonding usually dominates)
d7 - d7 Single bond
d8 - d8 No bond (symmetry interaction)
 Sabhuku Mudavanhu
Metal-Metal Bonding 3
Note that the table on the previous page specifically refers to two
square-planar metals interacting as shown in the MO diagram. Metal
centers with other geometries can often adopt M-M bond orders
different from that shown in the table. Electron-counting can often
provide some guidance on this. Although, if you don’t have any d
electrons, you generally can’t have any M-M bonding. Nor can you
have a higher M-M bond order than the # of d electrons being shared
between the metal centers. For example, two d2 metals could only form
a maximum of a M=M double bond.
Some Covalent Multiple Bonded Examples:
Double Bonds
R
t-Bu t-Bu
O O R
Cl Cl
Cl Cl O O
Ta Ta Cl Os Os Cl
O O
O Cl Cl O
R O O

R
Ta=T a = 2.68 Å Os=Os = 2.30 Å

Triple Bonds
d 5-d 5 Tr iple Bond
Chisholm d 3-d 3 Tr iple Bonds
O
PhH2C OC C
CH2Ph
PhH2 C
Mo Mo Cr Cr
CH2 Ph
PhH2C C C
CH2Ph O O

Mo-Mo = 2.17 Å Cr-Cr = 2.27 Å

 Sabhuku Mudavanhu
Metal-Metal Bonding 4
Quadruple Bonds (Cotton)
d4-d4 electronic configurationsoften lead to the formation of quadruple
M-M bonds. Prof. F. Albert Cotton at Texas A&M is famous for his
discovery and extensive studies of M-M quadruple bonds (and other M-
M bonded systems).

Me Me
O O
4
Cr Cr
F. Albert Cotton
Cr-Cr = 1.85 Å Texas A&M University

View down Re-Re axis showing

eclipsed geometry

H3C CH3 2-
H 3C Re CH3

H3C CH3
Re
H 3C CH3

Re-Re = 2.18 Å

An important orbital feature of quadruple bonds is that they have

eclipsed D4h-like ligand conformations. This is clearly illustrated above
for the non-bridged [Re2(CH3)8]2 complex. There is clear steric
repulsion between the methyl groups that could be relieved by rotation
to a staggered geometry. But the -bond component of the quadruple
bond favors an eclipsed orientation and imposes a rotational barrier for
rotations about the quadruple bond. Triple bonds do not have this
rotational barrier (free rotation!), thus the M≡M triple bonded
complexes on the previous page have staggered geometries.
 Sabhuku Mudavanhu
Metal-Metal Bonding 5
Dative M-M Bonds (unsymmetrical M-M bonded complexes)
When a metal center with at least two d electrons and a moderately high
electron count (16 or 18e-) is adjacent to a metal that is unsaturated and
electron-deficient, the more electron-rich metal center can donate a lone
pair of d electrons to the unsaturated metal to form what is called a
dative M-M bond. This is usually indicated by using an arrow ( )
instead of a line for a covalent bond.
Consider the following bimetallic nickel complex:
t-Bu t-Bu
Ni-P = 2.16 Å Ni-P = 2.24 Å
P
planar coordination CO tetrahedral coordination
like Ni(+2) OC Ni Ni like Ni(0)
CO
P
Ni-CO = 1.70 Å Ni-CO = 1.78 Å
t-Bu
t-Bu

Ni-Ni = 2.41 Å
There are two ways of viewing this electronically (see table below) symmetrically
dividing the +2 charge on the nickels needed to balance the two anionic
phosphide ligands giving you two d9 Ni(+1) oxidation state metals, a covalent Ni-
Ni bond, and 16 and 18e- metal centers.

Covalent M-M Bonding Dative

Left Ni Right Ni Left Ni Right Ni
Ni(+1) d9 Ni(+1) d9 Ni(+2) d8 Ni(0) d10
[-PR2] 2e- [-PR2] 2e- 2[-PR2] 4e- 2-PR2 4e-
-PR2 2e- -PR2 2e- CO 2e- 2CO 4e-
CO 2e- 2CO 4e- Ni←Ni(0) 2e-
M-M 1e- M-M 1e-
Total 16e- Total 18e- Total 16e- Total 18e-
The other method is to note that the one nickel has tetrahedral coordination
geometry, just like a d10 Ni(0) center, while the other nickel has a planar
geometry similar to a d8 Ni(+2) center. One can “assign” the two negatively
charged phosphide ligands with the Ni(+2) center and have them acting as
“neutral” 2e- donors to the Ni(0) center. This then gives one an 18e- Ni(0) center
 Sabhuku Mudavanhu
Metal-Metal Bonding 6
and a three-coordinate 14e- Ni(+2) center. Let the electron-rich, 18e- d10 Ni(0)
center donate one of its’ lone pairs to the unsaturated 14e- d8 Ni(+2) bringing it
up to 16e-, which is a normal electron-count for a square-planar d8 Ni(+2) atom.
Note that we get the same electron count and some sort of Ni-Ni bond via either
method. So you generally don’t have to worry about which method you use.
Obviously, the covalent method is simpler.
The reason that many consider the dative M-M bond method to be more
“accurate” is that if both nickel atoms are classified as Ni(+1), why don’t both
have the same geometry? One could explain the differences in geometry &
structural features simply because one Ni has an extra CO coordinated and we
will have an electronically unsymmetrical complex regardless of the oxidation
state assignments.

Problem: Electron-count the following complex using both the

covalent and dative M-M bonding methods:
R2
Me3P
P CO CO
Me3P
W Re
CO
Me3P
CO OC CO

Problem: Electron-count the following

PR3
complex. What is the order of the Re-Re
bond? Why wouldn’t it be appropriate Cl Re Cl
to use the dative bond method for this R3P
complex?
R3P Re Cl

Cl PR3
 Sabhuku Mudavanhu
Metal-Metal Bonding 7
Weak M-M Interactions by Symmetry
Based on the MO diagram at the beginning of this section, d8-d8 systems
shouldn’t have any M-M bonding due to the filling of
all the M-M antibonding orbitals, which cancels out the
M-M bonding orbitals.
But Harry Gray and others noted that more than a few
bi- or polymetallic d8 complexes do show the presence
of weak M-M bonding interactions, both in solution and
the solid-state. Harry Gray
Caltech
For example, the Rh and Ir tetrakis(isocyanide)
complexes, [M(CNR)4]+, form oligomeric M-M bonded stacks in
solution and in the solid-state, in spite of the fact
C NR that there should be no covalent M-M bonds.
RNC Ir CNR
RNC Gray proposed in 1974 that these persistent, but
R P
3
Ir Cl weak M-M interactions were caused by a
RN
C CN
R molecular orbital symmetry interaction between
the filled -M-M bonding and *-anti-bonding
C NR
RNC Ir CNR orbitals with the empty pz  and * orbitals. The
RN C empty orbitals are pushed up in energy and the
filled orbitals down in energy by this symmetry
interaction. This generates a weak M-M L L
bond – strong enough, however, to L L
M M
allow these complexes to form M-M L L
bonds even in solution. This orbital L L

effect is shown in the MO diagram to 

the right. pz pz



dz 2 dz 2


 Sabhuku Mudavanhu
Ligand Substitutions 1

Reaction Mechanisms - Ligand Substitutions

A substitution reaction is one in which an existing ligand on a metal

center is replaced by another ligand. Exactly how this occurs depends
on the electron count of the metal complex, the existing ligands on the
metal, and their steric and electronic properties.

MLn + xP MLn-xPx + xL
The mechanism of this substitution will almost always depend on
whether the parent MLn complex is coordinatively saturated or not!

Cavet: “A mechanism is a theory deduced from the available

experimental data. The experimental results are facts;
the mechanism is conjecture based on those facts”
Lowry & Richardson

“You can never prove that your mechanism is right -

only wrong.”
Guy in the audience asking
about your proposed mechanism

Substitutions reactions occur by a combination of ligand addition and

ligand dissociation reactions.
Saturated Complex: Dissociative Pathway!
Unsaturated Complex: Associative Pathway (usually)
Dissociative pathway (sometimes)
Most of the substitutions we will study will involve 2e- pathways. Odd
e- or radical pathways are known, but less common.
 Sabhuku Mudavanhu
Ligand Substitutions 2
Ligand Addition (association): this is when an incoming ligand
coordinates to a metal center that has one or more empty orbitals
available. Ligand Addition
Ph3P Ph3P Cl
Rh Cl + CO Rh
Ph3P OC PPh3

This Rh(+1) complex is d8 and only 14e-. Adding a ligand takes one to
the more stable 16e- square-planar complex.

Ligand Dissociation: this is when a ligand coordinated to a metal

dissociates (falls off). The probability of a specific ligand dissociating
depends on how strongly or weakly it is coordinated to the metal center
and stericLigand
effects.
Dissociation

Ph3P Cl Ph3P
Rh Rh Cl + PPh3
Ph3P PPh3 Ph3P
The steric hindrence of the three bulky PPh3 ligands favors dissociation
of one to form the 14e- RhCl(PPh3)2 complex. The moderate
electron-donating ability of the PPh3 ligand (not a strongly coordinating
ligand) makes this fairly facile.

Me2 Cl Me2 Me2 Cl Me2

P P P P
Ru Ru + Cl
P P P P
Me2 Cl Me2 Me2 Me2

The strongly donating ability of the dmpe ligands combined with their strong
chelate effect makes it difficult to dissociate one of the PMe2 arms. In this
case the Cl- anion is the one that dissociates, leaving a cationic complex
behind. The two dmpe ligands donate enough electron-density to the Ru
center to make it reasonable to dissociate a Cl-.

A ligand substitution can occur either by an associative or

dissociative route. The exact mechanism depends in large part on the
electron-count of the metal complex undergoing the ligand substitution.
The simplest case is when one is dealing with an 18e- metal complex.
In this case one almost always has a dissociative substitution. In a
dissociative substitution, one of the existing ligands on the metal center
 Sabhuku Mudavanhu
Ligand Substitutions 3
has to fall off (ligand dissociation), this opens up a free coordination
site (16e-, if one started from an 18e- complex) to which the new ligand
can coordinate.
O O O
C C C
-CO +PMe3
OC CO OC CO OC CO
Mo Mo Mo
OC CO OC CO OC CO
C PMe3
O
18e- saturated 16e- unsaturated 18e- saturated
complex complex complex

18e- complexes almost always do ligand substitutions through initial

ligand dissociation. Dissociative substitution can also occur in 16e- (or
in very unusual cases, lower electron count systems) complexes. These
cases either involve sterically bulky ligands that block the open
coordination site, or third row square planar d8 complex like Pt(+2)
where there are strong electronic factors that limit the coordination of an
additional ligand to the empty axial site.
-PCy3 +PMe3
Cl PCy3 Cl Cl PMe3
Ni Ni Ni
Cy3P Cl Cy3P Cl Cy3P Cl
16e- unsaturated 14e- unsaturated 16e- unsaturated
complex complex complex

The large PCy3 ligands sterically block access to the empty axial pz orbital

Shown to the left are perpendicular

views of space filling models (showing
the sizes of the atoms) of HRhCl(PMe3)2
(top) and HRhCl[P(t-Bu)3]2 (bottom).
Color coding: Rh – purple, Cl – green, P
– orange, C – white, H – cyan. Note
how the much bulkier tert-butyl groups
on the phosphines effectively block out
the empty axial orbital on the metal
(purple atom). In order to do a ligand
substitution the HRhCl[P(t-Bu)3]2
complex needs to dissociate one of the
other ligands first – probably either the
P(t-butyl)3 or the chloride.
 Sabhuku Mudavanhu
Ligand Substitutions 4
In the following example, the filled and spatially extended Pt dz2 orbital
can act as an electronic block:
-Cl +Br
Cl PPh3 Cl PPh3 Cl PPh3
Pt Pt Pt
Ph3P Cl Ph3P Ph3P Br
+Br
Br
-Cl
Cl PPh3 Cl PPh3
Pt Pt
Ph3P Cl Ph3P Br
T he spatially extended filled axial Pt d z2 orbital partially blocks coordination of ligands via
the empty axial pz orbital. T his limits ligand association, although it can occur.

Problem: The rate of substitution reactions on square planar d8

complexes goes in the order: Ni > Pd >> Pt. Explain why.

Steric Factors
Bulky (large) ligands occupy more space around a metal center and can
block incoming ligands trying to access vacant coordination sites on a
metal. Due to steric hindrance, however, they are also more often to
dissociate to relieve the steric strain. Consider, for example, the
following equilibrium:
KD
Ni(PR3)4 Ni(PR3)3 + PR3
25ºC

Ligand: P(OEt)3 P(O-p-tolyl)3 P(O-i-Pr)3 P(O-o-tolyl)3 PPh3

Cone angle: 109º 128º 130º 141º 145º

KD : < 1010 6 x 1010 2.7 x 105 4 x 102 > 1000

Note that there is virtually no Ni(PPh3)4 in solution. There is too much

steric hindrance with the bulky PPh3 ligands. Note that steric effects
often turn on very suddenly – that is, you don’t see much effect and then
wammo!
 Sabhuku Mudavanhu
Ligand Substitutions 5
Problem: There is also an electronic effect in the previous example
that favors PPh3 dissociation. What is it?

Solvent Effects
Consider the following dissociative substitution rxn discussed earlier:
-Cl + solvent
Cl PPh3 Cl PPh3 Cl PPh3
Pt Pt Pt
Ph3P Cl Ph3P - solvent Ph3P solvent

+Br
Cl PPh3
Pt
Ph3P Br

The 14e- three coordinate intermediate is actually almost immediately

coordinated by a solvent molecule to produce the solvated 16e- complex
shown to the far right. The solvent is usually weakly coordinated and
readily dissociates to constantly produce the 14e- reactive intermediate.
Few organometallic chemists formally write solvated metal complexes
down in their mechanisms, but they certainly are formed.
The coordinating ability of the solvent, therefore, can often affect
reactions. The presence of lone pairs and electron-rich donor atoms on
the solvent usually makes it a better ligand. Some common coordinating
solvents are shown on the next page.
The polarity of the solvent can also have a definite impact on a reaction.
Polar solvents are usually quite good for reactions, such as that shown
above, involving charged species. A non-polar hydrocarbon solvent
(like toluene, for example) would probably inhibit the chloride
dissociation mechanism. Instead, the dissociation of the neutral, less
polar phosphine ligand would probably be favored.
 Sabhuku Mudavanhu
Ligand Substitutions 6
Some Common Coordinating Solvents

O
O O S
H3C CH3
H3C CH3 DMSO
acetone THF (dimethylsulfoxide)
(tetrahydrofuran) bp = 189ºC
mp = 18ºC

H3C OH N C CH3
OH
methanol
ethanol acetonitrile

O
O O
H NMe2 O H H
DMF DME water
(dimethylformamide) (dimethoxyethane) (rarely used)

bp = 153ºC
mp = -61ºC

Note that one often avoids oxygen containing solvents due to the
reactivity of early transition metals towards them. Water is rarely used
in organometallic chemistry since many of the reactive metal-alkyl
complexes are basic enough and will readily react with water.
Non-coordinating solvents are a misnomer since anything can
coordinate to a metal center that is unsaturated and electron-deficient
enough. But saturated hydrocarbons like hexane are classic “non-
coordinating” solvents. Arene solvents can coordinate via their -
systems, but usually not too strongly.
A common less coordinating, but polar solvent, is CH2Cl2, which is one
of the less reactive chlorocarbon solvents. Clorobenzene is another
relatively non-reactive, but somewhat polar solvent.
 Sabhuku Mudavanhu
Ligand Substitutions 7
Trans Effect
The trans effect concerns the electronic effect of one ligand on another
ligand when they are trans (opposite) to one another. The classical
trans effect involves two -donating ligands trans to one another. The
stronger -donor ligand preferentially weakens the bond of the weaker
-donor ligand trans to it, making it easier to dissociate and do a ligand
substitution reaction.

-Cl N N
Cl PEt3 PEt3 PEt3
Pt Pt Pt
Et3P L Et3P L Et3P L

Relative rate of substitution based on trans ligand L :

Cl = 1, Ph = 100, CH3 = 103, H = 104

There is a cis effect, but it is much weaker and basically ignored:

-Cl N
Et3P Cl Et3P Et3P N
Pt Pt Pt
Et3P L Et3P L Et3P L

Relative rate of substitution based on cis ligand L :

Cl = 1, Ph = 2, CH3 = 4, H = 4

Note that when most chemists talk about the trans effect they are
referring to the - type of trans effect, where a strong -donor
weakens the -donating ligand trans to it.
Do NOT overestimate the importance of the trans-effect. As you
will see on the following pages there are other forms that have
different effects.
 Sabhuku Mudavanhu
Ligand Substitutions 8

-Acceptor Trans Effects

But there are other types of electronic trans effects that involve -
backbonding ligands. We will focus here on CO ligands as the most
common type.
The bonding of a -backbonding ligand to a metal with two or more d
electrons is weakened when there is a trans -backbonding ligand. The
competition of both -backbonding
ligands for the same d orbital electrons
reduces the amount of -backbonding
that can occur and, therefore, weakens
the M-CO bond strength.
Conversely, a -backbonding ligand bonding to a metal is strengthened
by being trans to a good -donating
ligand that can’t -backbond.
Compare the CO infrared stretching
frequencies for the following two
complexes:
Complex CO cm1 The P(OMe)3 ligand has about the same
Mo(CO)3[P(OMe)3]3 1977, 1888 -donor ability as pyridine, but is a
Mo(CO)3(pyridine)3 1888, 1746 considerably better -acceptor ligand,
thus completing with the trans CO
ligands more than the pyridine ligands.
There is a further strengthening of M-CO -backbonding when the trans
ligand has -donation properties that can push up the energy of the filled
d orbitals and, in turn, make them better -donors to the CO. This can
occur even when the ligand is not an especially strong donor.
 Sabhuku Mudavanhu
Ligand Substitutions 9

An example of this can be seen in the following three complexes and

their “anomalous” CO stretching frequencies:
PPh2 PPh2

Ph2P PPh2 Ph2P S Ph2P O

Rh Rh Rh

OC I OC I OC I

CO = 2011 cm-1 CO = 1987 cm-1 CO = 1983 cm-1

Even though the trans PPh2 is a better -donor than the P=S, or
certainly the P=O ligand, the “-pushing” effect mentioned above
enhances the trans CO -backbonding for the P=S and P=O ligands.
Problem: Consider the following series of substitution reactions.
O O
C C PMe3 PMe3
OC CO PMe3 OC CO PMe3 OC CO PMe3 OC PMe3
Cr Cr Cr Cr
OC C O 25°C OC PMe3 80°C
OC PMe3 110°C OC PMe3
C C C C
O O O O

As one replaces each CO ligand with a PMe3, the next CO

substitution is progressively more and more difficult requiring
higher temperatures and longer times. Once one forms
Cr(CO)3(PMe3)3, it is extremely difficult to replace another
carbonyl ligand. Why?
 Sabhuku Mudavanhu
Ligand Substitutions 10
Associative Substitutions
These occur first by a ligand addition to the metal complex followed by
the dissociation of one of the original ligands. You typically need to
have an unsaturated (17e- or lower) complex in order to propose an
associative substitution mechanism.
PMe3
+PMe3 -PPh3
OC PMePh2 OC PMePh2 OC PMe3
Rh Rh Rh
Ph2MeP Cl Ph2MeP Cl Ph2MeP Cl
16e- unsaturated 18e- saturated 16e- unsaturated
complex complex complex
-Cl
OC PMePh2
This rxn could proceed by two different likely Rh
substitution routes. Cl- is not that strong a ligand Ph2MeP PMe3
and can be substituted off by stronger donating
neutral ligands like PMe3. 16e- unsaturated
complex
The filled axial Pt dz2 orbital partially blocks coordination of ligands via the empty axial pz orbital.
This limits, but does not stop ligand association, which is quite common for Rh(I) and Pd(II).

Although one could theoretically have a ligand addition to an 18e-

complex to form a 20e- transition state (or intermediate) that would then
dissociate a ligand to reform an 18e- system, there are very few verified
examples of this in the literature.
incoming ligand
O O
C L L
C
OC CO OC CO OC CO
Mo + L Mo Mo + CO
OC CO OC CO OC CO
C C C
O O about to be O
dissociated ligand

18e- complex 20e- transition 18e- complex

state with added
ligand

So associative substitutions are generally limited to 17e- and lower

electron-count systems where the incoming ligand is not sterically or
electronically blocked from bonding (coordinating) to the metal center.
 Sabhuku Mudavanhu
Ligand Substitutions 11
“AC/DC” Ligands
Multidentate ligands (those donate more than 2e- and occupy more than
one coordination site on a metal) can often change their coordination
number to donate fewer electrons, thus opening up a coordination site
that can allow an associative substitution (or just ligand addition).
The Cp ligand can do this by shifting from an 5 to 3 (or even 1)
coordination mode as shown in the example below:

H 1-Cp
Keq = 0.4
H3C PMe3
Casey &
Re + 2PMe3 Re coworkers
ON CH3 4°C Me3P PMe3
Me3P N
O PMe3
80°C 50°C
PMe3 PMe3 CH3
THF
Me3P PMe3
ON Re PMe3 Re
3-Cp Me3P PMe3
0-Cp
Me3P CH3 N
O

But shifting the 5-Cp to the 3-Cp coordination mode incurs a

moderately high energy cost due to the loss of aromaticity in the Cp
ring. So this is not that common.
Indenyl Effect
The indenyl ligand family, however, shows dramatically enhanced
substitution reactions due to the ability to switch the aromaticity
between the Cp and arene ring via the following resonance structures:

indenyl resonance/aromaticity switch

 Sabhuku Mudavanhu
Ligand Substitutions 12

This dramatically lowers the barrier for the to resonance 5-Cp 3-Cp
structure, opening up a free coordination site and allowing far easier
ligand additions and substitution reactions.

+ PPh3

Rh Rh Rh
OC CO OC CO OC PPh3
C
O

- CO

Rh Rh
OC PPh3 OC PPh3

Consider the following relative rates of ligand substitution using the

following Cp-class ligands:
Me Me Me
Me Me
Ligand: Me Me
Me
Me
Me
Me Me

Relative rate of
substitution: > 1010 3.8 x 108 6.1 x 105 1 2.2 x 102

The fluorenyl ligand accelerates the ligand substitution reaction by a

factor of over 1010 !! Holy Cow!
Although the indenyl effect should theoretically generate great catalysts
due to the ability to readily open up free coordination sites on the metal,
it also, unfortunately, makes the indenyl ligand considerably easier to
substitute off the metal completely.
 Sabhuku Mudavanhu
Ligand Substitutions 13
Pentadienyl
The pentadienyl ligand is an acyclic version of Cp that does not have
any aromatic stabilization. This has two important effects:
1) No aromatic stabilization means that the -orbitals are higher in energy and
are, therefore, better donors than Cp. Similarly, the *-antibonding orbitals
are lower in energy and are better -acceptors than Cp (but the low
electronegativity limits the amount of -backbonding that can occur).
2) The lack of aromatic stabilization means that there is a much smaller barrier
for 5-pentadienyl 3-pentadienyl 1-pentadienyl
transformations.

Bleeke & coworkers

PMe3 PMe3 Me3P PMe3

Re Me3P Re PMe3 Re
Me3P
PMe3 Me3P PMe3
Me3P Me3P PMe3 PMe3

5 3 1

Allyl
The allyl anion has a similar facile ability to switch between 3 and 1
coordination modes that can promote ligand additions and/or
substitutions.
O O O O
C C C C
+L - CO
CO CO CO CO
Mn Mn Mn Mn
CO CO L CO CO
C C C L
O O O

3 1 1 3
usually not observed can be stable
experimentally and isolated
 Sabhuku Mudavanhu
Ligand Substitutions 14
Nitrosyl
We usually count the nitrosyl ligand as a cationic 2e- donor,
isoelectronic with CO. But it can adopt an anionic 2e- configuration
with a bent coordination geometry:

metal has n M N O M N metal has n-2

electrons electrons
O

This can occasionally lead to interesting behavior where the linear to

bent, cationic to anionic electronic state can open up a coordination site
on the metal by essentially oxidizing it (shuttling 2e- from the metal to
the NO+ turning it into NO). Given the extremely strong -
backbonding ability of NO+, this isn’t particularly surprising. The linear
NO+ form can usually be easily differentiated from the bent anionic
form by IR spectroscopy because of the large change in NO bond order
(triple to double bond).
O
O O O N
N N N N +L
Fe Fe O O N Fe L
C C C C C C
O O O
O O O
18e- (Fe2 ) 16e- (Feo ) 18e- (Feo )
 Sabhuku Mudavanhu
Ligand Substitutions 15
Radical Odd Electron Systems
17e-
One typically sees fairly dramatic rate enhancements for ligand
substitution reactions of 103 to 107 compared to 18e- systems.
18e- molten
PPh3
[V(CO)6] + PPh3 no reaction !
150°C

[V(CO)6] + PPh3 [V(CO)5(PPh3)] + CO

-70°C
17e-

The mechanism for the 17e- [V(CO)6]• radical is believed to be

associative to give a 19e- complex. The 19e- configuration weakens and
labilizes one of the V-CO bonds allowing a CO to dissociate, dropping
the complex back to a 17e- configuration.
This is supported by the following experimental data:
Rate = k[V(CO)6]• [PPh3] (second order)

 S‡ = 28 J/mol K (negative entropy indicates ordered transition state)

This is a general observation for most odd electron complexes studied.

The key is that the 19e- configuration is not as unstable as a 20e-
electron count that places 2e- into a M-L antibonding orbital. In a 17e-
complex, one electron is actually going into either a M-L bonding or
non-bonding orbital, while the next electron goes into the M-L
antibonding orbital. This makes the associative ligand addition
considerably easier compared to an 18e- system.
 Sabhuku Mudavanhu
Ligand Substitutions 16
Electron Transfer Catalysis (ETC)
One can “force” a stable, kinetically inert 18e- complex into a
considerably more reactive state by oxidizing it to a 17e- configuration,
thus opening up half a free orbital to which a ligand can bind initiating a
ligand substitution reaction. The metal can then be reduced back to the
18e- state.
Or one could reduce the metal to an unstable 19e- state, which would
labilize off the weakest coordinated ligand taking the metal complex
down to a more reasonable 17e- count. The metal center can then be
oxidized back to a 16e- state, giving an open orbital for a new ligand to
coordinate to.
This is usually done electrochemically and since there is no net change
in the number of electrons on the metal (oxidation is followed by
reduction), it is considered a catalytic substitution reaction. An example
is shown below.

- 1e + PPh3
Mn Mn Mn
N PPh3
N CO N CO C
Me C
Me
C C Me
C C C O
O O O
18e- 17e- 19e-

- NCMe

+ 1e
Mn Mn
OC PPh3 OC PPh3
C C
O O
18e- 17e-
 Sabhuku Mudavanhu
Ligand Substitutions 17

Problem: One could use electron transfer catalysis (ETC) to further

activate the very inert trans-Cr(CO)3(PMe3)3 complex that we
discussed earlier for another CO substitution. To initiate the ETC
you can either oxidize the complex to [Cr(CO)3(PMe3)3]+ or reduce
it to [Cr(CO)3(PMe3)3]. Only one of these would be likely to
substitute off a CO ligand to replace it with a PMe3 ligand. Which
one would you use and why?
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 1

Oxidative Addition
An oxidative addition reaction is one in which (usually) a neutral ligand
adds to a metal center and in doing so oxidizes the metal, typically by
2e-. The transferring of the two electrons from the metal to the
incoming ligand breaks a bond in that ligand forming two new anionic
ligands. At least one of these new anionic ligands ends up bonded to the
metal center.
two new anionic
hydride ligands

H H H
OC PPh3 +H2 OC PPh3 OC PPh3
Ir Ir Ir
Ph3P Cl Ph3P Cl Ph3P H
Cl
Ir(+1) Ir(+1) Ir(+3)
16e- 18e- 18e-

There are three main classes of molecules (substrates) that can perform
oxidative additions to metal centers: non-electrophillic, non-
electrophillic “intact”, and electrophillic.
Non-electrophillic: these molecules do NOT contain electronegative
atoms and/or are not good oxidizing agents. Aside from H2, they are
often considered to be “non-reactive” substrates. These molecules
generally require the presence of an empty orbital on the metal center
in order for them to pre-coordinate prior to being activated for the
oxidative addition rxn.
H2, C-H bonds, Si-H bonds, S-H bonds,
B-H bonds, N-H bonds, S-S bonds, C-C bonds, etc.
H2 is by far the most important for catalytic applications, followed by
Si-H bonds, B-H, N-H, and S-H bonds. C-H bond activation and
functionalization is very important, but still not practical.
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 2

Non-electrophillic “Intact”: these molecules may or may not

contain electronegative atoms, but they do need to have a double or
triple bond present. One needs a metal center with an empty orbital
(16e- or lower count) in order to pre-coordinate the ligand before the
oxidative addition occurs.
Unlike most of the other substrate molecules that break a single bond
and form two separate anionic ligands upon the oxidative addition, these
ligands have double or triple bonds and only one of the -bonds is
broken leaving the -bond intact. The ligand does pick up two electrons
from the metal and becomes a dianionic ligand.
Typical “intact” ligands that can perform an oxidation addition without
fragmenting apart are (O2 can also act as an electrophillic substrate):
alkenes, alkynes, and O2
One often needs to have electron withdrawing functional groups on the
alkenes or alkynes in order to “soup-up” their electron-withdrawing
ability in order to help promote the transfer of electrons from the metal
to the ligand.
metallocyclopropene
R
R R PMe3
PMe3
Me3P Pt Pt
PMe3
-PMe3 PMe3
R
In this case we have oxidized the Pt center from Pt(0) d10 to Pt(+2) d8
and generated a new dianionic unsaturated alkenyl ligand. Note that we
have broken one of the alkyne -bonds.
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 3

Electrophillic: these molecules do contain electronegative atoms and

are good oxidizing agents. They are often considered to be “reactive”
substrates. These molecules do NOT require the presence of an empty
orbital (18e- is OK) on the metal center in order to perform the
oxidative addition rxn.
X2 (X = Cl, Br, I), R-X, Ar-X, H-X, O2, etc.
The most common substrates used here are R-X (alkyl halides), Ar-X
(aryl halides), and H-X. An example of the oxidative addition of
CH3Br to IrCl(CO)(PPh3)2 is shown below. Note that the starting metal
complex in this case is 16e-:
SN2 nucleophillic attack
+ 
  H
Ph3P CO
+CH3Br
OC PPh3 C Br
Ir Ir
Ph3P Cl H
Cl PPh3 H

Ir(+1) Ir(+1)
16e- 16e-
two new anionic
two new anionic ligands
ligands
CH3 CH3
OC PPh3 +Br OC PPh3
+ Br
Ir Ir
Ph3P Cl Ph3P Cl
Br
Ir(+3) Ir(+3)
18e- 16e-

Note that the H3C-Br bond is broken on the oxidative addition reaction
generating two new anionic ligands: CH3 and Br. If the starting
metal complex is 16e- (as shown above) both ligands will usually end up
coordinated to the metal to make an 18e- complex.
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 4

In the case of a starting 18e- complex (shown below) only one of the
two anionic ligands (usually the strongest binding) generated from the
oxidative addition will end up coordinated to the metal unless a separate
substitution reaction occurs.
oxidative
CO H H
addition OC CO
OC
+ Cl
OC Re + Cl OC Re
OC CO
OC CO
two new anionic
ligands
Re(-1) -CO Re(+1)
18e- 18e-
OC CO
1) CO ligand dissociation
OC Re 2) 1- to 3-allyl hapticity change

OC

Re(+1)
18e-

In this case the alkyl anion is the best donor ligand and easily “beats
out” the more electronegative and poorly donating Cl anion. Note that
the alkyl ligand (-CH2CH=CH2) initially coordinated to the Re after the
oxidative addition is an 1-allyl ligand and that it can convert to the
generally more stable 3-allyl on CO ligand dissociation.
General Features of Oxidative Additions
Because oxidative addition involves oxidation (removal of electrons) of
the metal center, the more electron-rich the metal is the easier the
oxidative addition to the metal center will be. So in comparing two or
more metal complexes to see which will be the most reactive towards a
particular substrate for oxidative addition you would pick the metal
center with the strongest donor ligands, fewest -acceptor ligands, or
most negative charge. Also remember that the non-electrophillic ligands
(Class A) and “intact” ligands (Class C) usually require that there is an
empty orbital (16e- or lower) on the metal center in order to react.
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 5

Kinetic Data for Oxidative Addition Reactions of MX(CO)(PR3)2

Rate Const H‡ S‡
M X PR3 Reactant (M1 sec1) (kcal/mol) (J/mol K)
Ir Cl PPh3 H2 0.67 10.8 23
Br 10.5 12.0 14
I > 100
Ir Cl PPh3 O2 3.4 x 102 13.1 21
Br 7.4 x 102 11.8 24
I 30 x 102 10.9 24
Ir Cl PPh3 CH3I 3.5 x 103 5.6 51
Br 1.6 x 103 7.6 46
I 0.9 x 103 8.8 43
Ir Cl P(p-C6H4-OMe)3 CH3I 3.5 x 102 8.8 35
P(p-C6H4-Cl)3 3.7 x 105 14.9 28
Rh Cl PPh3 CH3I 12.7 x 104 9.1 44
P(p-C6H4-OMe)3 51.5 x 104 10.2 43

Data adapted from “Principles and Applications of Organotransition Metal Chemistry”, Coleman,
Hegedus, Norton & Finke, University Press, 1987; refs: Chock & Halpern, JACS, 1966, 88, 3511; Ugo,
Pasini, Fusi, Cenini, JACS, 1972, 94, 7364; Douek & Wilkenson, J. Chem. Soc. (A), 1964, 2604. Rxns
generally run in benzene at 25ºC.

Notice the trends in the table above. The more electron-rich the metal center
(better donating ligands) the faster the oxidative addition reactions. The one
exception is the oxidative addition of
CH3I with the Ir-Cl, Br, I series of
complexes. The slow down is caused by
steric factors caused by the increase in
size of the halide affecting the
nucleophillic attack of the metal dz2
orbital on the CH3I to start the oxidative
addition reaction.
The space-filling figures show two different views of the Ir-
Cl (left) and Ir-I (right) complexes. The top view is looking
down on the square plane with the halide oriented to the
left. The bottom view is looking down the halide-Ir axis and
illustrates how the larger size of the iodide causes more
steric interactions with the phenyl rings on the PPh3
restricting their rotation. The PPh3 phenyl rings as shown
in the top view partially block the axial coordination site.
The larger size of the iodide causes pushes the phenyl
rings more towards the metal causing more steric hindrance
for incoming substrates.
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 6

WARNING: d0 metals can NOT do oxidative additions!! So always

electron count the starting and final metal complexes to check out the
overall electron-count, metal oxidation state and d-electron count!

Oxidative additions are easy to identify IF YOU ELECTRON

COUNT the metal complexes. When an oxidative addition rxn occurs
the metal will be oxidized, usually by 2e-. So, if you start with a metal
in the 0 oxidation state (d8), after the oxidative addition the metal will be
in the +2 oxidation state (d6). Once you get used to looking at
organometallic rxns you will be able to identify common oxidative
additions quite quickly. H2, R-X, and H-SiR3 are three of the most
common substrates that perform oxidative addition reactions in
catalytic cycles.

Problem: H2 will do an oxidative addition most readily to which of

the following complexes. Why?

a) b)
(MeO)3P Cl Me3P Br
Ir Rh
OC P(OMe)3 OC PMe3

O
c) C

Pt CO
Me3P
PMe3
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 7

Problem: Cl2 will do an oxidative addition most readily to which of

the following complexes. Why?
a) b) PMe3
CO
OC CO
Re Pd PMe3
OC CO Me3P
CO PMe3

c)
Cl
Ti
Cl

Problem: CH3Br will do an oxidative addition most readily to

which of the following complexes. Why?
a) O b) PMe3

Hf Pt NCMe
NR2
Me3P Me3P
NR2 NCMe

c) CO
(PhO)3P CO
Fe
OC P(OPh)3
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 8

Oxidative Coupling
Consider the following reaction:

Ph2
Cl Ph2
Cl
P P
H3C N Cr H3C N Cr
P P
Ph2 Cl Ph2 Cl

Cr(+3) d3 Cr(+5) d1
15e- 13e-

The Cr on the right now has two new anionic alkyl ligands forming a
metallocyclopentane ring system. We have done an oxidative addition,
but in forming a new bond between the two ethylene ligand (and losing
the original double bonds) we have coupled the two ligands together.
While this is an oxidative addition, there is a special term for this type of
reaction called oxidative coupling. The metal is being oxidized to
create two new anionic ligands, but the original two neutral ligands also
form a new bond between them, instead of fragmenting apart to make
two new independent anionic ligands.
The driving force for this reaction is the formation of a new C-C -bond
(stronger than a -bond) and the creation of two new strongly donating
anionic ligands that can better donate to the metal even though one has
technically lowered the electron count.
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 9

Reductive Elimination

A reductive elimination reaction is the reverse of an oxidative addition.

It is a reaction in which two cisoidal anionic ligands on a metal center
couple together. Each anionic ligand pushes one electron back onto the
metal center (in the case of a monometallic complex) to reduce it by 2e-.
The coupled anionic ligands then usually fall off the metal center as a
neutral molecule.
two cisoidal anionic ligands that
can form a bond between them and eliminate
a neutral
ligand
H H H
OC PPh3 OC PPh3 OC PPh3
Ir Ir Ir + H2
Ph3P H Ph3P Cl Ph3P Cl
Cl
Ir(+1) Ir(+1)
Ir(+3) 18e- 16e-
18e- rarely observed intermediate metal reduced
by 2 e-

Since electron-rich metal complexes favor oxidative addition, the

reverse is true for reductive elimination. Since reductive elimination
involves pushing electrons back onto the metal center from two anionic
ligands that are usually more electronegative than the metal center, it is
best if the metal center is electron deficient. This can be accomplished
by having electron-withdrawing ligands (e.g., CO), cationic charge(s),
and/or coordinative unsaturation (sub-18e- counts).
While reductive elimination can occur from saturated 18e- complexes
(so long as the two ligands that you want to reductively eliminate are
cisoidal to one another), it has been shown that reductive elimination
can be promoted by a ligand dissociation generating an unsaturated and
more electron-deficient metal center.
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 10

CH3 CH3
Ph2
P CH3
-I Ph2
P CH3
Ph2
P CH3
Pt Pt Pt + CH3CH3
P
Ph2 I
CH3
 P
Ph2
CH3 P
Ph2

Pt(+4) Pt(+4) Pt(+2)

18e- 16e- 14e-

+I
The dissociation of the I- generates Ph2
P CH3
a cationic unsaturated complex. This Pt Goldberg, J. Am. Chem. Soc.
is electron deficient enough to help P I 1995, 117, 6889-6896
promote the reductive elimination of Ph2
ethane (CH3CH3).
Pt(+2)
16e-

In studying the above system, it was also found that one could have
reductive elimination of CH3I from the starting 18e- complex. This
reaction, however, is very reversible due to the high reactivity of CH3I
for doing an oxidative addition back reaction with the electron-rich
neutral Pt(+2) complex to make the Pt(+4) octahedral compound.

reductive elimination The reductive elimination of the CH3I is

kinetically favored. This is because the
Ph2
CH3 Ph2 orbitals around the iodide anion are
P CH3 P CH3
spherically symmetric and this makes
Pt Pt + CH3I
P
Ph2 I
CH3
 P
Ph2
CH3 it much easier to overlap with the alkyl
group orbital to perform the reductive
elimination. The sp3 directed orbitals
Pt(+4) Pt(+2) on the two CH3 groups are more difficult
18e- 16e- to overlap in order to get the reductive
elimination to occur. But the reductive
oxidative addition elimination of the CH3CH3 is thermo-
dynamically considerably more favorable
and the back oxidative addition much
more difficult.
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 11

Problem: Which of the following compounds will be most likely to

do a reductive elimination of ethane (CH3-CH3)? Why?

a) CH3 b) NCMe
Me3P CH3 (MeO)3P CH3
V Os
Me3P CO H3C P(OMe)3
CO NCMe

c) PMe3
MeCN CH3
Pt
Ph3P CH3
CH3

Problem: Which of the following mechanisms makes the most sense

for the indicated reductive elimination (direct route or dissociative
route via a cationic intermediate)? Why?

a) CH3
Me3P CH3 Me3P CH3
Pt Pt + H3C CH3
Me3P CH3 Me3P I
I

b) CH3 CH3
Me3P CH3 Me3P CH3
Pt Pt + I
Me3P CH3 Me3P CH3
I

Me3P CH3
Pt + H3C CH3
Me3P I
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 12

Binuclear Systems
Complexes with two (or more) adjacent metal atoms can also participate
in oxidative addition and reductive elimination reactions. This often
involves both metal centers. If so, then each metal changes its oxidation
state by only ±1, instead of ±2 as occurs with single metal centers.
This also often involves the making or breaking of a M-M bond,
depending on what is present in the starting complex.
Cl
Cl Cl
Au Au Au
+ Cl2
Me2P PMe2 + Cl2 Me2P PMe2 Me2P PMe2
Au Au Au
Cl Cl Au-Au = 3.1Å
Au-Au = 3.0Å Au-Au = 2.6Å Cl
Au(+1) d10 Au(+2) d9 Au(+3) d8

Below is a somewhat usual case of a C-C bond oxidative addition to a

dimetal unit. The reverse reaction could also be considered a reductive
coupling instead of a reductive elimination since the ligand stays
coordinated to the metal center:
O O
C C

h Ru Vollhardt, JACS,
Ru-Ru = 2.82Å Ru Ru 1983, 105, 1676.
Ru
O
C C C C
O
 C
O O O C
O
Ru(+1) d7 Ru(+2) d6

The next two examples involve reductive eliminations across a

bimetallic unit:
D3C CD3 D3C
CH2 H2C CH2 D
-hydride Me2N NMe2
O O elimination O O O O
Mo Mo Mo Mo Mo Mo
Me2N Me2N - CH2=CD2 Me2N Me2N
+ D3C CH2D
bimetallic reductive
O O O O elimination O O

NMe2 NMe2 NMe2 Chisholm

& coworkers
3
Mo(+3) d Mo(+3) d3 Mo(+2) d4
16e- 16e- 14e-
 Sabhuku Mudavanhu
Oxidative Addition/Reductive Elimination 13

In general bimetallic reductive eliminations occur across two metals

when there is a M-M bond and when one can have good overlap of the
two groups orbitals. Notably, there are very few if any examples of two
alkyl groups performing a bimetallic reductive elimination.
CH3 CH3 M M
or + H3C CH3
M M M M

CH3 H M M
or + H3C H
M M M M

This is due to the very poor overlap of the directed sp3 hybrid orbitals on
the alkyls used to bond to the metal centers. Alkyl and hydride
eliminations have been observed, no doubt due to the spherically
symmetric orbital on the hydride that can overlap with the carbon sp3
hybrid orbital promoting the reductive elimination. The reductive
elimination of two hydrides is well known and quite common. Stanley’s
proposed hydride-acyl bimetallic reductive elimination (below) is also
reasonable due to favorable overlap of the sp2 acyl and hydride orbitals.

Problem: Which of the two bimetallic complexes shown below will

be most likely to do a reductive elimination of H2? Why?
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 1

Migratory Insertion
A migratory insertion reaction is when a cisoidal anionic and neutral
ligand on a metal complex couple together to generate a new
coordinated anionic ligand. This new anionic ligand is composed of the
original neutral and anionic ligands now bonded to one another.
General Features:
1) No change in formal oxidation state (exception: alkylidenes)
2) The two groups that react must be cisoidal to one another
3) A vacant coordination site is generated by the migratory insertion.
Therefore, a vacant site is required for the back elimination reaction (e.g.,
-hydride elimination). A trapping ligand is often needed to coordinate to
the empty site formed from a migratory insertion in order to stop the back
elimination reaction.
4) Migratory insertions are usually favored on more electron-deficient metal
centers.

migratory insertion ligand addition

acyl
O O CH3 O CH3
C
OC CO OC CO +L OC CO
Mn Mn Mn
OC CH3 OC OC L
C C C
O O O
Mn(+1) Mn(+1) Mn(+1)
18e- 16e- 18e-
elimination

The following are common anionic and neutral ligands that can do
migratory insertion reactions with one another:
Anionic: H, R (alkyl), Ar (aryl), acyl, O2 (oxo)
Neutral: CO, alkenes, alkynes, carbenes
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 2

CO and alkyl migratory insertions (as shown above) are extremely

important and are often generically referred to as carbonylation
reactions. Hydride and CO migratory insertions to produce formyl
groups are not common due to the thermodynamic instability of the
formyl-metal interaction.

Some Electronic effects

R O Z
R
Z
CO CO
OC Fe +L OC Fe
CO THF L
C C
O O
best Lewis acid - can coordinate to electron-rich
CO ligands and drain off some e- density

Z+ = Li+ > Na+ > (Ph3)2N+

strongest coordinating ligand - best trapping ligand

L = PMe3 > PPhMe2 > PPh2Me > CO

most electron-rich alkyl group makes the best nucleophile for
migrating to the electron-deficient CO
R = n-alkyl > PhCH2

Note that the acyl ligand formed is not as good a donor compared to the
starting alkyl. But the metal has gained (replaced) an electron
withdrawing CO ligand with a better donating phosphine. Thus, the
overall reaction with a trapping ligand is usually towards the migratory
insertion.
The reason that more electron-deficient metals favor CO-alkyl migratory
insertions is that makes the carbon atom of the CO more electrophillic
and susceptible to nucleophillic attack from the more electron-rich alkyl
group.
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 3

Migration vs. Insertion

There are two different “directions” that a migratory insertion can occur.
A migration is when the anionic ligand moves and performs a
nucleophillic-like intramolecular attack on the electrophillic neutral
ligand. An insertion is when the neutral ligand moves and “inserts” into
the bond between the metal and anionic ligand. Both of these pathways
are illustrated below:
Migration

O O CH3
C a MIGRATION rxn involves the
OC CO OC CO anionic ligand doing a
Mn Mn nucleophillic-like attack on the
OC CH3 OC neutral ligand. This involves the
C C anionic ligand moving to the site
O O where the neutral ligand is
coordinated. An empty
Mn(+1) Mn(+1) coordination site is left behind.
18e- 16e-
Insertion
O
C an INSERTION rxn involves the
OC CO OC CO neutral ligand moving over to
Mn Mn O where the anionic ligand is
OC CH3 OC coordinated and "inserting" into
C C the anionic ligand-metal bond to
CH3 generate the new anionic
O O
ligand. An empty coordination
Mn(+1) Mn(+1) site is left behind from where
18e- 16e- the neutral ligand originally was
located.

While most systems studied have been shown to do migrations, both are
possible. The following example shows a system where both are very
similar in energy and the solvent used favors one or the other.
inversion

Et migrates
*CO Fe*
Fe*
CH3NO2 Ph3P Ph3P C*O
Et O Et O
Fe*
Ph3P Et
C
O HMPA *CO
Fe* Fe* O
O Ph3P
CO inserts Ph3P
*C
Et O Et
retention
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 4

We generally do NOT worry about the exact pathway, that is why we

use the redundant term “migratory insertion” to indicate that either
directional pathway is fine and we don’t know (or care) exactly how the
reaction is proceeding. Many organometallic chemists short-cut this and
just say insertion reaction. They do not usually mean that they know
what the mechanism is.

Alkene Migratory Insertions

Alkene and hydride/alkyl migratory insertions are also extremely
important and an example is shown below:

CH3 CH3
Zr Zr Zr

CH3

CH3
Zr Zr

CH3

This is the basis for almost all transition metal-based polymerization

catalysts. A polymerization rxn is just many, many migratory insertions
of an alkene and alkyl (the growing polymer chain) interspaced with
alkene ligand addition reactions.
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 5

An alkene and a hydride usually react via a migration of the hydride to

the coordinated alkene ligand:
migratory insertion

H
H H H H ‡ H
H
H H H H H H

M H M H M

-hydride elimination

The backwards reaction, of course, is a -hydride elimination and is

usually quite favorable if there is an empty orbital cis to the alkyl ligand.
Thus, the general importance of having a trapping ligand to coordinate
to the empty orbital generated from the migratory insertion.
Bercaw and coworkers demonstrated via spin saturation NMR
techniques that the Nb-H-alkene complex shown below was constantly
performing a migratory insertion, but that the final produce was only
observed when a trapping ligand was added to the reaction mixture.

* * *
H CO CO
Nb R Nb Nb
R
H R
* * H
*
N MR ir r adiat ion of t he Nb-hy dr ide r esonance af f ects the NMR r esonance f or t he alk yl hydr ide,
demonst rating t hat t hey ar e connect ed by t he migr at or y inser tion mechanism

Problem: Why don’t either of the complexes shown below do

alkene-hydride migratory insertions at room temperature?
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 6

H
Cl PPh3
Et3P
Ir Pt
Ph3P CO
H PEt3

Problem: Sketch out and label the two mechanistic steps (in the
correct order) that are occurring for the following reaction.

Ru + PPh3 Ru
H Ph3P
C C
O O

Alkynes can also do migratory insertions to produce vinyl groups as

shown below:
CH3
CH3
RCN PMe3 RCN PMe3 RCN PMe3
Rh Rh Rh
Me3P H Me3P H Me3P

CH3

An intramolecular alkyne migratory insertion to make a lactone ring

system:
O
O O
O
Ph3P O -PPh3 Ph3P O Ph3P +PPh3
Pd Pd Pd Ph3P
Cl PPh3 Me Cl Cl O Pd
O
Me Cl PPh3
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 7

Agostic C-H to Metal Interactions – “Frozen Migratory Insertion”

On occasion one can find an alkene-hydride migratory insertion that

doesn’t go all the way:

* * *
H H
Co + H+ Co Co
H H
R3P R3P
R3P

One of the C-H bonds of the methyl group is within bonding distance to the Co center.
This is called an Agostic C-H bond interaction.

Normally this is a transition state structure for a hydride-alkene

migratory insertion or a -hydride elimination. In some cases, however,
it can be observed as a ground-state stable structure.
Because the C-H bond is sharing some of its -bond electron density
with the metal, the C-H bond is weakened. This produces some
relatively clear-cut spectroscopic characteristics:
1) C-H infrared stretching frequency is lowered to the mid-2500 cm-1
region from a normal value of 2900-3000 cm-1
2) the JC-H coupling constant in the 13C NMR is lowered to around 70-
90 Hz from a normal value of 150 Hz.
3) the 1H chemical shift of the agostic proton is in the 10 to 15 ppm
region, much like a metal-hydride resonance.

Also note that since the agostic C-H bond is in between a migratory
insertion and a -hydride elimination, small changes in steric or
electronic factors on the metal can push it one way or the other. Also
since the agostic C-H bond to metal interaction is usually fairly weak,
the addition of a better ligand can displace usually in the direction of the
M-alkyl complex.
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 8

Carbene Migratory Insertions

Carbene (or alkylidene) ligands can also do migratory insertions with
adjacent anionic ligands:
X L X
M CH2 + L M CH2

X = H, R, OR, halide

Note that we have somewhat of an electron-counting problem here.

Normally a migratory insertion refers to a neutral ligand reacting with an
anionic ligand to produce a new anionic ligand. But if we electron-
count the carbene as a dianionic ligand, we are reacting a monoanionic
ligand (X) with a dianionic ligand (carbene) to make a new monoanionic
ligand. This changes the oxidation state of the metal center and is now
formally what we would call a reductive coupling reaction (since the
metal is being reduced and we are coupling together two ligands).
What most people do is to consider the carbene (or alkylidene) as being
a neutral ligand. That resolves the electron-counting “problem.”
Note also that in the case of X = H, the reverse reaction is called an -
hydride abstraction or elimination.
Ph3C+ = good hydride abstracting reagent

* * *
+ Ph3C+
Re Re Re

H3C
CH3 H H3C CH2
Ph3P Ph3P Ph3P

*
Re
H
Ph3P
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 9

Ph3C NCMe
Ph Ph NCMe
W W W
CH3 H CH2 CH2

Ph

Note that these are reactive “carbenes” and not heteroatom stabilized.
They are also probably more Schrock-like, but somewhat electrophillic
(note the presence of positive charge on both examples). Fischer
carbenes with heteroatoms would probably not be reactive enough for
these types of migratory insertion reactions.

Eliminations
Elimination reactions are just the reverse of migratory insertion
reactions. The various common elimination reactions are as follows:
H
H H
H -hydride elimination
M
M

H H
H -hydride elimination
M M
R
R

O
R carbonyl elimination
M or decarbonylation
M CO
R
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 10

The key points to remember are:

1) No change in formal oxidation state (exception: alkylidenes)

2) You must have an empty orbital that is cisoidal to the group that you are
doing an elimination reaction on. Alternatively, a cisoidal labile ligand
that can easily dissociate to open up an empty orbital.

One of the hardest elimination reactions is the breaking of a C-C bond.

For example the following migratory insertion is quite common and
plays a critical role in polymerization catalysis:
migratory insertion
H
 H
H H H H ‡ H
H H H H H CH3
M CH3 M CH3 M


But the reverse methyl elimination rxn is very difficult:

methyl elimination
H
H
H H H ‡ H H
H H H H Very
CH3 H
Difficult!
M M CH3 M CH3

rotation of C-C
bond to move CH3 CH3
group away from H
H H H
metal to avoid steric H H CH3
effects H
M M H
-hydride elimination

One reason for this is that the C-C -bond is surrounded by more
reactive C-H bonds that short-circuit the attack on the C-C bond and can
instead give a -hydride elimination. The directed nature of the sp3
hybridized C-C -bond also makes overlap with the empty metal orbital
quite difficult.
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 11

One unusual example of what is believed to be a methyl elimination

reaction is involved in the following transformation (Bergman, JACS,
2002, 124, 4192-4193):
* *
Rh + HSiPh3 Rh + CH4
Me3P N Me3P C
H3C C H3C N
CH3 SiPh3

The proposed mechanism for this reaction is shown below:

* * *
- NCCH3 - CH4
+ HSiPh3 + NCCH3
Rh Rh Rh
Me3P Me3P SiPh3 Me3P
N N
H3C C H 3C H Ph3Si C
CH3 Rh(+5) CH3

SiPh3 Rh
Rh N SiPh3
N C
Note that the isocyanide ligand is
C
more strongly donating and a better H3C CH3
-backbonding ligand than the starting
acetonitrile. This keeps this from being
a catalytic reaction.

methyl ligand
* elimination * dissociation *
Rh Rh N SiPh3 Rh
Me3P C Me3P Me3P
C C
H3C N CH3
SiPh3 N
H3C
Ph3Si

One reason that the methyl elimination reaction occurs here is that the -
hydride elimination reaction generates a high energy ketene-imine:
* *
N SiPh3
Rh N SiPh3 Rh C
Me3P Me3P
C
H H2C
H3C
 Sabhuku Mudavanhu
Migratory Insertion/Elimination 12

Problem: Identify each step in the following mechanism. Some steps

may have several things occurring.

1 2
* * *
Co Co Co
H3C H
H3C
H3C H3C

* CH2=CH2
PMe3
+ CH4 +
Co 3
Me3P

Problem: Sketch out a detailed mechanism and label each step for
the following overall reaction.

Rh + 2CO Rh
Ph3P OC
CH3 PPh3
H3 C

+
O

H3C CH3
 Sabhuku Mudavanhu
Catalysis Intro 1
Summary of Industrial Catalytic Processes
Process Typical Catalysts
Petroleum Refining
Cracking Pt/Re on alumina, Zeolites
Reforming Pt/Re/Ge/Sn on alumina (dehydrogenation)
Hydrocracking alumina, zeolites, Pt
Alkylation H2SO4, HF
Hydrodesulfurization (Mo-Co) oxides, (Mo-Ni) oxides
Hydrodenitrogenation (W-Ni) oxides
Chemical Manufacturing
Natural Gas desulfurization ZnO, Cu, Fe on activated C
Hydrogenations Raney Ni, Raney Co, Pt, Rh
Ammonia synthesis promoted Fe
Methanol synthesis Cu-ZnO
Dehydrogenation Butadiene: Fe2O3, Pt/Re on alumina
styrene: Zn, Cr, Fe or Mn oxides
Oxidations ethylene oxide: Ag
nitric acid: Pt/Rh mesh/gauze
sulfuric acid: V2O5
maleic, phthalic anhydrides: V2O5
formaldehyde: Ag or Cu; Mo, Fe, V oxides
Polymerizations Ziegler-Natta polypropylene: Al alkyls + TiCl3
Dow single site polypropylene: Ti metallocene
Phillips -- Cr oxide on silica
Polyethylene (low density): peroxides, peresters
Polystyrene: benzoyl peroxide
Urethanes: amines, organo-tin, phosphine oxides
Hydroformylation Union Carbide/Hoechst/BASF: Rh/PPh3
Exxon/BASF: HCo(CO)4
Shell: HCo(CO)4(PR3) (R = bulky alkyl)
 Sabhuku Mudavanhu
Catalysis Intro 2
Catalytic Production of the Top Organic Industrial Chemicals
Ranking Chemical Production
#4 Ethylene Steam Cracking of Hydrocarbons:
larger hydrocarbon smaller hydrocarbon + H2
C2H6(g) C2H4(g) + H2(g)
33 billion lbs Catalyst: Zeolites, Pt/Re on Al2O3 support
Conditions: 850°C, 20-50 atm
#10 Propylene Steam Cracking of Hydrocarbons:
C3H8(g) C3H6(g) + C2H4(g) + CH4(g) H2(g)
Catalyst: Zeolites, Pt/Re on Al2O3 support
18 billion lbs Conditions: 850°C, 20-50 atm
#12 Dichloroethane Direct Chlorination:
C2H4(g) + Cl2(g) ClCH2CH2Cl(g)
Catalyst: FeCl3 or AlCl3
15 billion lbs Oxychlorination:
2C2H4(g) + 4HCl(g) + O2 2ClCH2CH2Cl(g) + 2H2O
Catalyst: Cu salts on SiO2 or Al2O3 supports
#16 Benzene Hydrocarbon Reforming (dehydrogenation)
C6H14(g) C6H12(g) + H2(g) Endothermic!
C6H12(g) C6H6(g) + 3H2(g) Endothermic!
10 billion lbs toluene benzene + methane
Catalyst: Pt/Re/Ge/Sn on Al2O3 support
#17 Ethyl Benzene C6H6(g) + C2H4(g) C6H5C2H5
1. Catalyst: Liquid phase system with AlCl3
9 billion lbs 2. Catalyst: Zelolite – Lewis Acid based gas phase process
Classic Friedel-Crafts rxn.
#19 Vinyl Chloride ClCH2CH2Cl(g) H2C=CHCl(g) + HCl(g)
This reaction is often coupled with the oxychlorination reaction
to produce dichloroethane, this allows recycling of the HCl.
8 billion lbs
#20 Styrene Dehydrogenation of ethyl benzene
Catalyst: Fe oxides on Al2O3 support
8 billion lbs Conditions: 550-600°C
#21 Terephthalic Acid Amoco Process:
p-CH3-C6H4-CH3 + 3O2 p-HOOC-C6H4-COOH + H2O
Catalyst: Co/Mn salts (with some heavy metal bromides)
8 billion lbs
Conditions: liquid acetic acid solution, 200°C, 20 atm
Ti or Hastelloy C lined reactor (very corrosive)
 Sabhuku Mudavanhu
Catalysis Intro 3
#22 Methanol CO + H2 CH3OH
Catalyst: ZnO/Cu salt
7 billion lbs Conditions: > 100 atm, 200-300°C
#24 Ethylene Oxide C2H4(g) + ½O2 ethylene oxide
Catalyst: Ag
6 billion lbs Conditions: 300°C
#26 Toluene Catalytic Reforming of methyl cyclohexane and derivatives
Catalyst: Pt/Re on Al2O3 support
6 billion lbs Conditions: 500°C and 25 atm
#27 Xylenes Catalytic Reforming of 1,4-dimethylcyclohexane
Catalyst: Pt/Re on Al2O3 support
5.5 billion lbs Conditions: 500°C and 25 atm
#28 Ethylene Glycol ethylene oxide + H2O HOCH2CH2OH
Catalyst: H2SO4 (0.5 - 1%), 50°-70°C
5 billion lbs Conditions: Thermal @ 195°C and 15 atm.
#29 Butylaldehyde Hydroformylation -- Union Carbide/Celanese/BASF
propylene + H2 + CO CH3CH2CH2CHO

5 billion lbs Catalyst: homogeneous Rh/PPh3 catalyst

Conditions: 100-125°C, 8-25 atm
#31 Cummene benzene + propene C6H5CH(CH3)2
1. Liquid phase catalysts: H2SO4, AlCl3, HF
3.7 billion lbs 2. Gas phase catalyst: H3PO4 on SiO2
Friedel Crafts reaction
Conditions: 35-40ºC, 7 bar (liquid); 200-300ºC, 20-40 bar (gas)
Cumene is mainly used to produce phenol and acetone.
#32 Acetic Acid CH3OH + CO CH3COOH
Catalyst: homogeneous RhI2(CO)2
(Monsanto Acetic Acid process)
3.5 billion lbs
Conditions: 150°C, 35 atm
 Sabhuku Mudavanhu
Catalysis Intro 4

Homogeneous Catalysis

[catalyst]
A + B C
Remember that thermodynamics and equilibrium still rule!! A catalyst
only speeds up the rate at which a chemical reaction reaches
equilibrium. The actual equilibrium constant (thermodynamics) is NOT
affected by the catalyst. Therefore, non-spontaneous reactions are
usually NOT suitable for catalytic applications.

Advantages/Disadvantages of Homogeneous Catalysts Relative to

Heterogeneous Catalysts
Good homogeneous catalysts are:
good generally far more selective for a single product
far more active
far more easily studied from chemical & mechanistic aspects
far more easily modified for optimizing selectivity
bad far more sensitive to permanent deactivation
far more difficult for acheiving product/catalyst separations

Heterogeneous catalysts dominate chemical and petro-

chemical industry: ~ 95% of all chemical processes use
heterogenous catalysts.
Homogenous catalysts are used when selectivity is critical
and product-catalyst separation problems can be solved.
 Sabhuku Mudavanhu
Catalysis Intro 5

Homogeneous or Heterogeneous?
Because many homogeneous catalysts decompose to form
heterogeneous catalysts, and some heterogeneous catalysts can dissolve
to form homogeneous catalysts, one should always be careful about
making assumptions on what type of catalyst one is using in any new
catalytic experiment. There are several general ways to test whether a
catalyst is homogeneous or heterogeneous.
1) Exposure to elemental Hg will generally poison a heterogeneous
catalyst
2) Exposure to polythiols will poison most homogeneous catalysts
3) Light scattering studies to identify the presence of colloids
(heterogeneous)
4) Product selectivity studies
e.g., polymer bound alkenes:
Catalyst
Polymer + H2 Polymer

Catalyst Homo/Hetero % Yield

RhCl(PPh3)3 homo 100
Ni(OAc)2 + NaBH4 hetero --
[Rh(nbd)(PR3)2]+ homo 90
Pd/C hetero --
[Ir(cod){P(i-pr)3}(py)]+ homo 100
 Sabhuku Mudavanhu
Catalysis Intro 6
Some Catalysis Terminology

Turnover (TO) -- one loop through the catalyst cycle. Typically one
equivalent of reactant is converted to one equivalent of product (per
equivalent of catalyst).
Turnover Frequency (TOF) or Turnover Rate -- the number of passes
through the catalytic cycle per unit time (typically sec, min or hrs). This
number is usually determined by taking the # of moles of product
produced, dividing that by the # of moles of catalyst used in the
reaction, then dividing that by the time to produce the given amount of
product. The units, therefore, are usually just time1. Note that the rate
of a batch catalytic reaction is fastest at the very beginning of when the
reactant concentration is the highest and generally slows down as the
reaction proceeds -- stopping when all the reactant is used up. Note the
graph below for the production of aldehyde product from the
homogeneously catalyzed reaction of vinyl acetate, H2, and CO.
Vinyl Acetate Hydroformylation sampling from
0.3mM catalyst -- 85°C/90 psi H 2/CO autoclave causes
2,000 pressure glitches
1,800
4.5
Uptake curve
1,600
4
1,400
Equiv 1,200 -1 3.5
kobs = 0.0076 min
Aldehyde Ln  P)
1,000 3
Prod Ln plot
800
2.5
600 Initial TOF
2
400 8 TO/min
476 TO/hr
1.5
200

0 1
0 5 10 15 20
Time (hours)

The TOF, therefore, will vary throughout the course of a batch reaction.
The Initial TOF is defined as the initial part of a catalytic reaction
where the rate is the fastest and essentially linear. A far better measure
 Sabhuku Mudavanhu
Catalysis Intro 7
of rate is the observed rate constant kobs, which allows one to reproduce
the entire product production curve given a set of reactant & catalyst
concentrations. In the above graph, the reaction is pseudo-first order in
excess reactant alkene (vinyl acetate concentration ~ 0.6 M, catalyst 0.3
mM) and kobs is determined from a ln plot of the change in H2/CO
pressure (reactant concentration) versus time for this rxn. When
reporting kobs chemists often normalize it to a certain catalyst
concentration (1 mM, for example).
Turnover Number (TON) -- the absolute number of passes through the
catalytic cycle before the catalyst becomes deactivated. Academic
chemists sometimes report only the turnover number when the catalyst
is very slow (they don’t want to be embarassed by reporting a very low
TOF), or decomposes quite rapidly. Industrial chemists are interested in
both TON and TOF. A large TON (e.g., 106 - 1010) indicates a stable,
very long-lived catalyst. TON is defined as the amount of reactant
(moles) divided by the amount of catalyst (moles) times the % yield of
product. Authors often report mole % of catalyst used. This refers to
the amount of catalyst relative to the amount of reactant present. 10
mole % = 10 TO, 1 mole % = 100 TON, 0.01% = 10,000 TON.
ee (enantioselectivity) – this defines the enantioselectivity of an
asymmetric catalyst that produces more of one optically active
enantiomer (R enantiomer, for example) than the other (S enantiomer).
ee is defined as:

RS
ee  100%
RS
A catalyst that makes an equal amount of R and S enantiomers has 0%
ee (a racemic mixture). 85% or higher is generally considered a good
ee, although that depends on what the best known catalyst can do
relative to that being reported.
 Sabhuku Mudavanhu
Catalysis Intro 8
Catalysis Data in Publications
There is a lot of mediocre/bad catalysis reported all the time in
chemistry publications. One often has to dig into the data to figure this
out. The things one wants to typically look for to tell whether there is
“good” catalysis or not include:
1) # of turnovers performed – more is better
2) TOF (turnover frequency) – faster is better
3) Good selectivity for the product – this includes chemoselectivity,
regioselectivity, and enantioselectivity (if applicable)
4) Reaction conditions – harsh? Mild? Unusual? Concentrations?

To figure out the number of turnovers you need to know the amount of
substrate (reactant) and catalyst:
# moles (equivalents) reactant (substrate)
Turnovers 
# moles (equivalents) catalyst

But authors often list these values in different ways and you may have
to do some interpreting. The most common alternate way of
representing the substrate:catalyst ratio is mole %. This is especially
common for organic chemists doing Pd-catalyzed coupling reactions.
10 mole % catalyst means that there is 10% as much catalyst as
substrate on a molar basis. This is equivalent to 10 turnovers.
10 mole % catalyst = 10 turnovers These represent the
theoretical maximum #
5 mole % catalyst = 20 turnovers of turnovers. One also
has to note the % yield
or the % conversion of
1 mole % catalyst = 100 turnovers substrate into product to
figure out the actual # of
0.1 mole % catalyst = 1000 turnovers turnovers!!

0.01 mole % catalyst = 10,000 turnovers

 Sabhuku Mudavanhu
Catalysis Intro 9
Example: Consider the following catalytic data reported in a J. Am.
Chem. Soc. communication (very prestigious) a number of years ago:
O
R + CO + H2O HO R
Hydrocarboxylation

Let’s look at the last line of data from the table since that had the
highest ee. The third column contains the important information about
the ratio of reactant (often referred to as substrate), chiral chelating
ligand L*, and PdCl2.
The authors had 7.7 equivalents of reactant, 0.38 equivalents of chiral
ligand, and 1 equivalent of Pd. This means that the maximum number
of turnovers they could do is defined by the amount of reactant (moles
or equivalents) divided by the amount of catalyst (moles or equivalents).
equivalents reactant 7.7
max turnovers    7.7
equivalents catalyst 1.0
 Sabhuku Mudavanhu
Catalysis Intro 10
7.7 turnovers is small and not at all impressive. Hydrocarboxylation,
however, is a difficult catalytic reaction and doing it asymmetrically is
even more impressive.
Of course, 7.7 turnovers assumes 100% yield, which they did not get.
The actual number of turnovers needs to be reduced by the % yield,
which they report as 64%, so the actual number of turnovers is:
actual turnovers  7.7  0.64  4.9
4.9 turnovers is barely catalytic. What about the TOF? Well you have
to read a little footnote to find how long they ran the reaction to get their
64% yield: 18 hours at 1 atm of CO. The TOF is the number of
turnovers divided by the time:
4.9 turnovers
TOF   0.27hr  1
18 hr
Well, 0.27 turnovers/hr is also barely catalytic. But that 91% ee is quite
impressive isn’t it. Or is it?
The authors only added 0.38 equivalents of chiral ligand to 1 eq of
PdCl2 to generate, at most, 0.38 equivalents of chiral catalyst (assuming
one ligand per Pd). This is rather unusual, since one usually adds a little
excess of chiral ligand to generate a chiral catalyst, even when dealing
with a chelating ligand. There are examples where one can add less
ligand than metal complex due to the fact that the metal-ligand catalyst
generated is much more active than the starting metal complex itself.
But one almost always adds enough ligand (or extra since the ligand can
dissociate) to generate as much of the presumed catalytically active
species as possible.
 Sabhuku Mudavanhu
Catalysis Intro 11
The ligand that the author is using is:

OH
O
P
O
O

BNPPA

This is being used under rather acidic conditions (typically needed for
Pd-catalyzed hydrocarboxylation) and under these conditions it is highly
unlikely that it would be able to function as a ligand. Remember that
the late transition metals don’t particularly like oxygen donor ligands
(weaker bonding).
This fact makes the high ee’s rather suspect. And a number of research
groups (Hoechst Celanese, Union Carbide, etc.) have found (although
not published) that the actual ee for this “catalyst” is close to 0.
So it is often important to read the experimental conditions very
carefully and with a critical eye.
 Sabhuku Mudavanhu
Catalysis Intro 12
Problem: Consider the following catalytic data reported in a recent
publication. What information is missing?
 Sabhuku Mudavanhu
Catalysis Intro 13
Problem: Beller and coworkers have reported (Angew. Chem., 2001, 40,
3408-3411) on hydroformylation catalysis using HRh(CO)(Naphos).
The table of catalytic data from their paper is shown below. For
experiment # 1, how many turnovers did the authors do? Clearly show
how you calculate your number. Is there any important data missing
from this table?
 Sabhuku Mudavanhu
Catalysis Intro 14

Problem: What information is missing from the following Table of

catalytic results (they defined the ligands used elsewhere in the paper).
How many turnovers are they doing?
 Sabhuku Mudavanhu

Hydrogenation Catalysis

Hydrogenation is the addition of H2 to a multiple bond (C=C, CC,

C=O, C=N, CN, N=O, N=N, NN, etc) to reduce it to a lower bond
order. The most common and simple type of hydrogenation is the
reduction of a C=C double bond to a saturated alkane:

R + H2 R

There are three different ways that transition metal catalysts can activate
H2 for performing hydrogenation catalysis:
H
LnM + H2 LnM oxidative addition

LnM-X + H2 LnM-H + HX hydrogenolysis

heterolytic
LnM + H2 + B: [LnM-H] + H+:B cleavage

Oxidative addition: the most common method of activating H2 on a metal with

d electrons (d2 or higher). Metal center typically needs to have an empty
coordination site in order to bind the H2 first, prior to the oxidative addition.
Hydrogenolysis: the only way that early transition metals with d0 counts can
activate H2. Lanthanides and actinides also typically use hydrogenolysis. As
with oxidative addition, the metal center needs to have an empty orbital to bind
the H2 and an anionic ligand (e.g., alkyl, halide) that can be protonated off. No
change in oxidation state of the metal.
Heterolytic cleavage: in many ways quite similar to hydrogenolysis except that
the proton produced does not directly react with an anionic ligand coordinated to
the metal, but rather with an external base that typically has to transfer it back to
the metal center to complete the catalytic cycle. Ru(+2) is the most common
metal that uses heterolytic cleavage as a mechanism. No change in oxidation
state of the metal.
 Sabhuku Mudavanhu
Hydrogenation 2
Wilkinson’s Catalyst: RhCl(PPh3)3 was the first highly active
homogeneous hydrogenation catalyst and was discovered by Geoffrey
Wilkinson (Nobel prize winner for Ferrocene) in 1964. R. Coffey
discovered it at about the same time while working for ICI (Imperial
Chemical Industries). It was very simply prepared by reacting RhCl3
3H2O with excess PPh3 in EtOH:
RhCl3·H2O + xs PPh3 RhCl(PPh3)3 + Ph3P=O + oxidzed solvent

The two initially proposed mechanistic routes are as follows:

 Sabhuku Mudavanhu
Hydrogenation 3
It has been clearly shown that PPh3 is readily lost due to steric crowding
and that the inner catalyst cycle with a weakly coordinated solvent
molecule is about 1000 times faster than the outer cycle that has 3 PPh3
ligands coordinated to the metal.
Osborn later discovered that cationic complexes like [Rh(cod)(PPh3)2]+
were considerably more active for hydrogenations relative to
Wilkinson’s catalyst. The reason for this is that the cationic metal center
is more electrophillic and this favors alkene coordination, which is often
the rate determining reaction step. Also by only having 2 PPh3 ligands
present one could keep the catalyst on the far more reactive catalytic
cycle.
Crabtree discovered that the cationic Ir catalyst, [Ir(cod)(PCy3)(Py)]+
(py = pyridine), was even more reactive. The Ru catalyst,
HRuCl(PPh3)3, is even more reactive for 1-alkenes. Rate data is shown
in the following table:
TOF (hr1)
Catalyst Temp ºC Solvent 1-hexene cyclohexene Me2C=CMe2
[Ir(cod)(PCy3)(py)]+ 0 CH2Cl2 6,400 4,500 4,000
[Ir(cod)(PMePh2)2]+ 0 CH2Cl2 5,100 3,800 50
[Ir(cod)(PMePh2)2]+ 0 acetone 10 0 0
[Rh(cod)(PPh3)2]+ 25 CH2Cl2 4,000 10 0
HRuCl(PPh3)3 25 C6H6 9,000 7 0
RhCl(PPh3)3 25 C6H6/EtOH 650 700 0
RhCl(PPh3)3 0 C6H6/EtOH 60 70 0

Alkene bulkyness also plays an important role with the following

general trend in hydrogenation rates:
R R R
R > R
> R R
>R >
 Sabhuku Mudavanhu
Hydrogenation 4
Ru Heterolytic H2 Activation
Ru has a strong tendency to perform a heterolytic activation of H2
instead of oxidative addition to make a metal dihydride. This can occur
either via hydrogenolysis or heterolytic cleavage mechanisms, giving the
same net result:
hydrogenolysis base trapping of HCl
prevents back rxn
PPh3 PPh3
Cl PPh3 Cl PPh3
+B:
Ru Ru + HCl B:H+ Cl
PPh3 Ph3P Cl Ph3P H
H
Cl
Ru
PPh3
+ B: + H2  H
Ph3P Cl 

PPh3 PPh3 PPh3

- BH+ -Cl
Cl PPh3 Cl PPh3 Cl PPh3
Ru Ru Ru
Ph3P Cl Ph3P Cl Ph3P H
 H H

 H
:B
heterolytic cleavage

Shown below is a proposed catalytic cycle for Ru(+2) catalyzed

hydrogenation:
PPh3
Cl PPh3
Ru
R + alkene
Ph3P H

PPh3 PPh3
Cl PPh3 Cl PPh3
Ru Ru
Ph3P Ph3P H
H R
 H R

PPh3
Cl PPh3
Ru
Ph3P
R

Note that there is no change in oxidation state of the Ru(+2)!

 Sabhuku Mudavanhu
Hydrogenation 5
Lanthanide Hydrogenation Catalysts
Tobin Marks reported the extraordinary activity of (Cp*2LuH)2 for the
hydrogenation of alkenes and alkynes. The monometallic complex
catalyzes the hydrogenation of 1-hexene with a TOF = 120,000 hr1 at 1
atm H2, 25ºC!! This is one of the most active hydrogenation catalysts
known.
The proposed mechanism is shown below:
* *
H
Lu Lu
H
* *

*
Lu
R H
*

* *
H H
Lu R
R Lu
H
* *

+ H2 *
Lu
R
*
 Sabhuku Mudavanhu
Hydrogenation 6
Selectivity:
Hydrogenation catalysts typically will selectively hydrogenate the most
reactive multiple bonds first. Steric and electronic effects play an
important role in this. Consider the following examples:
O O
RhCl(PPh3)3
+ H2 95%
25°C

RuCl2(PPh3)3
+ H2 > 90%
40°C

O O

1-octene

RhCl(PPh3)3
+ +
25°C

1-hexyne

Typically NOT hydrogenated under mild conditions:

O O
R C N - NO2
R H R R
 Sabhuku Mudavanhu
Hydrogenation 7
Directing Effects
Crabtree has demonstrated some very interesting substrate directing
effects in hydrogenation:

H2
+

HO i-Pr HO i-Pr HO i-Pr

Pd/C 20% 80%

[Ir(cod)(PCy3)(py)]+ 99.9% < 0.1%

The weak ligand bonding of the OH group on the substrate directs one
specific side of the alkene to coordinate to the metal center in order to
form an alkene-OH chelate to the Ir.
H
CH3
CH3 positive charge on Ir is important
R to attract the partial negatively
charged OH group. One also needs
O the presence of an empty orbital
H H
Ir

Group binding affinities: amide > OH > OR > ester ~ ketone

Amine groups bind too strongly and inhibit
catalysis. Rigid structures with stronger
chelates, like the norbornene ligand shown to the
right, are also poor substrates.

OH
 Sabhuku Mudavanhu
Hydrogenation 8
Asymmetric Hydrogenation
95% of all hydrogenations use heterogeneous catalysts like Pd on carbon
(Pd/C) or Raney Nickel (a highly porous form of Ni that is an excellent
and highly active hydrogenation catalyst). One area where homo-
geneous catalysis rules is asymmetric hydrogenation. This involves the
use of a chiral catalyst and an alkene substrate that generates a chiral
carbon center on hydrogenation.
The first dramatic example of this was reported in 1968 by Bill Knowles
and coworkers at Monsanto for the asymmetric hydrogenation of -
acetamidocinnamatic acid to produce L-Dopa, an important
pharmaceutical for the treatment of Parkinson’s disease.
OMe

P P dipamp

MeO

MeO COOH [Rh(dipamp)]+ MeO COOH

NHAc H NHAc
AcO AcO

H+
HO COOH

H NH2
HO

L-Dopa (S-Dopa)
97% ee

more to come !! (I’m still working on this section)

 Sabhuku Mudavanhu
Hydroformylation 1

Hydroformylation (Oxo) Catalysis

Aldehydes
O H O
Rh or Co
R +
R + CO + H2 H * R
linear (normal) branched (iso)
side reactions

R R
alkene isomerization alkene hydrogenation

* Largest homogeneous catalytic process

* > 15 billion pounds of aldehydes (alcohols) per year
* Commercial catalysts are complexes of Co or Rh
* Selectivity to linear (normal) or branched (iso)
products is important
Hydroformylation was discovered by Otto Roelen in
1938 during an investigation of the origin of
oxygenated products occurring in cobalt catalyzed
Fischer-Tropsch reactions. Roelen's observation that
ethylene, H2 and CO were converted into propanal,
and at higher pressures, diethyl ketone, marked the
beginning of hydroformylation.
Cobalt catalysts completely dominated industrial Otto Roelen (1897-1993)
hydroformylation until the early 1970's when rhodium
catalysts were commercialized. In 2004, ~75% of all hydroformylation processes
are based on rhodium triarylphosphine catalysts, which excel with C8 or lower
alkenes and where high regioselectivity to linear aldehydes is critical.
Most aldehydes produced are hydrogenated to alcohols or oxidized to carboxylic
acids. Esterfication of the alcohols with phthalic anhydride produces dialkyl
phthalate plasticizers that are primarily used for polyvinyl chloride plastics -- the
 Sabhuku Mudavanhu
Hydroformylation 2

largest single end-use. Detergents and surfactants make up

the next largest category, followed by solvents, lubricants
and chemical intermediates.

HCo(CO)4 Catalyst. Roelen's original research

into hydroformylation involved the use of cobalt salts
that, under H2/CO pressure, produced HCo(CO)4 as
the active catalyst. In 1960 and 1961 Heck and
Breslow1,2 proposed what is now accepted as the
general mechanism for hydroformylation: Richard Heck (b. 1931)

H
C O
O O C Co
C
O
H R C - CO
O + alkene

O O R
O O R H
C C C H CO C O
Co Co
O C Co Co C O H CO C
O
C C
C C
C O Monometallic O anti-Markovnikov
O O hydride addition
O to C=C bond to give
+ H2 Rate
Determining linear alkyl
- CO + CO
Step
H
C O O R
O C Co R
C + CO
O O O
C C C
O C Co O C Co
O C C
O O
Bimetallic C C
proposed bimetallic O O
pathway - NOT important
in normal catalysis
increasing the CO pressure keeps the back reactions from occuring -
3 atm CO = 1.6:1 L:B ratio this limits alkene isomerization and the corresponding opportunity for
90 atm CO = 4.4:1 L:B ratio making branched alkyl

An alternate bimetallic pathway was also suggested, but not favored, by Heck
and Breslow. The acyl intermediate could react with HCo(CO)4 to do an
intermolecular hydride transfer, followed by reductive elimination of aldehyde
producing the Co-Co bonded dimer Co2(CO)8. A common starting material for
HCo(CO)4 catalyzed hydroformylation, Co2(CO)8 is well known to react with H2
under catalysis reaction conditions to form two equivalents of HCo(CO) 4. The
 Sabhuku Mudavanhu
Hydroformylation 3

bimetallic hydride transfer mechanism is operational for stoichiometric

hydroformylation with HCo(CO)4 and has been proposed to be a possibility for
slower catalytic hydroformylation reactions with internal alkenes.3 The mono-
metallic pathway involving reaction of the acyl intermediate with H 2, however,
has been repeatedly shown to be the dominant mechanism for 1-alkenes and
cyclohexane.4,5
d (aldehyde)
 k[alkene][Co][H 2][CO] -1
dt
Kinetic studies support the HCo(CO)4 mechanism with a general rate
expression given above. The inverse dependence on CO pressure is
consistent with the mechanistic requirement for CO dissociation from
the various saturated 18e species to open up a coordination site for
alkene or H2 binding. When using a 1:1 ratio of H2/CO, the reaction
rate is essentially independent of pressure due to the opposing orders of
H2 and CO. Increasing the H2/CO ratio is of limited use for increasing
the overall reaction rate because HCo(CO)4 is only stable under certain
minimum CO partial pressures at a given temperature.
The reaction conditions for HCo(CO)4 hydroformylation are largely
governed by the thermal instability of HCo(CO)4, which produces
metallic cobalt if the CO 1000
partial pressure is not kept CO
Stable
Pressure
high enough. As the reaction (bar)
Region

temperature is increased, the 100

CO partial pressure required
Unstable
to maintain the stability of Region
HCo(CO)4 increases in a 10
100 150 200 250
logarithmic fashion (Fig. 1). Temperature °C
Thus, the temps needed for
Figure 1. Stability of HCo(CO)4/Co2(CO)8
reasonable reaction rates (110- species with respect to precipitation of cobalt
180° C) require rather high metal (cobalt concentration is 0.4 wt. %).
CO partial, and hence, total
H2/CO pressures of 200-300 bar.
 Sabhuku Mudavanhu
Hydroformylation 4

Increasing the CO partial pressure decreases the hydroformylation

reaction rate and the amount of alkene isomerization side reactions,
while increasing the aldehyde linear to branched product ratio. Pino
proposed that the apparent marked difference between HCo(CO)4
catalyzed hydroformylation at low and high CO partial pressures was
due to the existence of two active catalyst species, HCo(CO)4 and
HCo(CO)3, formed from the CO association/dissociation equilibrium:
HCo(CO)3 + CO HCo(CO)4
But the active catalyst is most likely the 16e- HCo(CO)3 complex.
The low probability of direct alkene reaction with the 18e- saturated
HCo(CO)4 catalyst is consistent with the reduced activity at higher CO
partial pressures. One can also explain the lower regioselectivity at
lower CO pressure by proposing that alkene isomerization is more facile
with the resulting 16e- RCo(CO)3 species that results after reaction with
alkene as shown below:
H
CO
Co alkene isomerization
CO
R C
O

H
OC CO CO OC CO
Co Co Co
CO CO CO
C
O R
R
linear alkyl
+CO
(leads to linear aldehyde)

O R

CO
OC Co branched acyl (leads to branched aldehyde)
CO
C
O
 Sabhuku Mudavanhu
Hydroformylation 5

Under lower CO partial pressures an unsaturated 16e- RCo(CO)3

will have a long enough lifetime to allow reverse -hydride elimination
and increase the possibility for alkene reinsertion to the branched alkyl
species, which is slightly more favored thermodynamically. At this
point CO addition and insertion will yield a branched aldehyde, or
another -hydride elimination can give alkene isomerization. This
second mechanistic explanation is in line with more recent results from
Rh/PPh3 catalyzed hydroformylation studies.
The regioselectivity of HCo(CO)4 (or HCo(CO)3) for producing the
more valuable linear aldehydes varies with reaction conditions and
alkene substrates used. With 1-alkenes one can typically get linear to
branched aldehyde ratios of 3-4 to 1. There is a trade-off between rate
and regioselectivity. High CO partial pressure slows the rate of
catalysis, but increases the linear to branched aldehyde product ratio.
Higher CO partial pressures also lower alkene isomerization side
reactions. Higher temperatures increase the reaction rate, but lower the
linear aldehyde product regioselectivity and increase various
undesirable side reactions. Some aldehyde hydrogenation to alcohols is
usually observed (5-12%), although alkene hydrogenation is usually
quite low (~ 1%), particularly under higher CO partial pressures.
Aldehyde hydrogenation is not considered to be a negative side reaction
because the aldehyde products are usually hydrogenated to alcohols in a
later reaction step. The aldehyde hydrogenation, however, consumes
additional H2, so H2/CO ratios greater than 1:1 are used (1-1.5:1 is
common).
High linear product regioselectivity is not, however, the major
concern for most HCo(CO)4 catalyzed industrial plants. What is now
Exxon Chemical Co. built the first United States hydroformylation plant
in 1948 in Baton Rouge, LA using the high pressure HCo(CO)4
technology confiscated from the Germans after WWII. This plant
produced over 540 million lbs of alcohols each year, and a new plant
came on line in 1994 which pushed the capacity to over 800 million lbs
 Sabhuku Mudavanhu
Hydroformylation 6

of alcohols a year. Exxon uses propylene dimerization/oligomerization

to produce a C7 to C12 mixture of branched internal alkenes. This
branched, internal alkene mixture is then hydroformylated and
hydrogenated to a C8 to C13 alcohol mixture. The alkene isomerization
ability of HCo(CO)4 is quite important in this situation. HCo(CO)4
under the proper reaction conditions is good at isomerizing double
bonds to essentially all possible locations. This can be clearly seen from
the data shown below that shows the % of aldehyde formed at each site
for the HCo(CO)4 catalyzed hydroformylation of 1-octene and 4-octene
(150° C/200 bar 1/1 H2/CO).6
22% 6% 22% 12%

65% 7% 55% 11%

% formyl group addition to indicated carbon

Under these conditions, the linear to branched aldehyde ratio for the
hydroformylation of 1-octene was 1.9:1. Starting with 4-octene one still gets a
1.2:1 linear to branched ratio. Thus, one can start with a considerably less
expensive mixture of terminal and internal alkenes and get a product distribution
favoring the linear aldehyde. The product distribution above can be nicely
explained by invoking facile alkene isomerization with the fastest
hydroformylation occurring for double bonds in the 1-position. Labeling studies
have shown that alkene isomerization generally occurs without dissociation of the
alkene from the cobalt catalyst.7
Alkene branching has a large effect on isomerization and hydroformylation.
In a study of various methyheptenes, Haymore found that there was very little
hydroformylation at the carbon center with the branch, even if it was part of the
double bond. Data for two methylheptenes and % of aldehyde formed at each site
is shown below.8 Note that isomerization past the branching carbon is not a
dominant reaction. Once again, terminal aldehydes are favored.
 Sabhuku Mudavanhu
Hydroformylation 7

4% 0% 2% 1% 0.2% 12%

72% 0.6% 6% 18% 5% 38%

0.5% 15% 25%

% formyl group addition to indicated carbon

Side reactions of the product aldehydes to

O - H2O O
form heavier products generally occur, 2
R R
H
particularly at higher reaction temperatures, condensation
H
R
and usually account for ~ 9% of the product
distribution. Aldol condensations, aldols, O OH O
2
trimerizations, and Guerbet dimerizations of R
H
R
H
aldol
product alcohols are some of the more R

common ways to form heavy byproducts. R

These side reactions occur to various extents O
R O
3
for all long term hydroformylations (Co or R
H
O
O
Rh). Although industrial reactors are usually trimerization

started with high boiling solvents, after a R

while these heavy “ends” become the main - H2O

2 R R
OH
solvent system for the reaction. OH
Guerbet
R

One advantage of the HCo(CO)4

technology is that catalyst separation and recycling is well established. BASF
oxidizes HCo(CO)4 with O2 to form water soluble Co2+ salts that are extracted
from the product stream. These Co2+ salts are recycled and reduced under
H2/CO to reform HCo(CO)4. Exxon uses aqueous NaOH to deprotonate
HCo(CO)4 after catalysis to make Na[Co(CO)4], which is extracted into an
aqueous stream. The active HCo(CO)4 catalyst is regenerated via use of H2SO4
and H2/CO.
 Sabhuku Mudavanhu
Hydroformylation 8

Cobalt Phosphine-Modified Catalysts. The only variation on

HCo(CO)4 hydroformylation catalysis involved research at Shell by
Slaugh and Mullineaux in which the addition of trialkylphosphine
ligands caused a dramatic change in the rate and regioselectivity.9 The
electronic effect of substituting an electron donating alkylated
phosphine for one of the carbonyl ligands to produce HCo(CO)3(PR3),
results in stronger Co-CO bonding. This causes a dramatic reduction in
the CO partial pressures required to stabilize the catalyst and prevent
formation of Co metal. Instead of 200-300 bars of H2/CO pressure
needed for HCo(CO)4, the monophosphine substituted HCo(CO)3(PR3)
only needed 50-100 bars of pressure, and could be run at higher
temperatures without any decomposition of catalyst to cobalt metal.
Another electronic effect is that the electron-donating phosphine
increases the hydridic nature of the hydride ligand (HCo(CO)4 is quite
acidic) and dramatically increases the hydrogenation capabilities of the
HCo(CO)3(PR3) catalyst. This means that the aldehydes produced are
subsequently hydrogenated by HCo(CO)3(PR3) to make alcohols. Less
e-rich phosphines, such as PPh3, give less hydrogenation to alcohol, and
lower linear regioselectivities. The better hydrogenation ability, how-
ever, also results in increased alkene hydrogenation side-reactions
producing alkanes that can range from 10-20% of the product
distribution (depending on the phosphine and rxn conditions). Because
of the aldehyde hydrogenation step more H2 is needed, so H2/CO ratios
of 2:1 (or slightly higher) are typically used. The proposed hydro-
formylation and hydrogenation mechanisms are both shown below.
 Sabhuku Mudavanhu
Hydroformylation 9

CO CO
+ CO O
OC Co OC Co

C PR3 C PR3
O R O
R
100-180°C
+ CO 50-100 atm
- CO
5-10 times slower
+ H2
R than HCo(CO)4
Hydroformylation
H H
O
OC Co H
OC Co
C PR3 - CO C PR3
O + alkene O
R

CO O
8:1 linear:branched
R' OH OC Co H R H

C PR3
alcohol O aldehyde

R'
H
O
H R'
H
OC Co H
OC Co O
Hydrogenation C PR3
C PR3 O
O

- CO R' + CO
CO
+ H2
OC Co O

C PR3
O
 Sabhuku Mudavanhu
Hydroformylation 10

The final electronic effect of phosphine substitution is that the higher

stability of the HCo(CO)3(PR3) catalyst, due to stronger Co-CO
bonding, means that this catalyst is less active than HCo(CO)4 (about 5-
10 times slower). Just as with the unmodified cobalt catalyst, CO
dissociation from the saturated 18e- species is needed to open up an
empty coordination site on the cobalt to allow coordination of alkene
and H2. Higher reaction temperatures, therefore, are used in
conjunction with longer reaction times and larger reactor volumes.
From a steric viewpoint the bulkier trialkylphosphine ligand favors
formation of linear products. While linear to branched ratios of only 2-
3:1 are typically found for HCo(CO)4, higher regioselectivities of 7-8:1
occur for HCo(CO)3(PR3). There is a phosphine cone angle cutoff at
about 132°, after which the phosphine ligand's steric effects do not
increase the product linear regioselectivity any further.
Table 1. Hydroformylation of 1-hexene using Co2(CO)8/2P as catalyst
precursor. 160°C, 70 atm, 1.2:1 H2/CO
Tolman  Cone kr x 103 % Aldehyde to
PR3 pKa (cm-1) Angle ° (min-1) Linear Prod alcohol
P(i-Pr)3 9.4 2059.2 160 2.8 85.0 --
PEt3 8.7 2061.7 132 2.7 89.6 0.9
PPr3 8.6 2060.9 132 3.1 89.5 1.0
PBu3 8.4 2060.3 136 3.3 89.6 1.1
PEt2Ph 6.3 2063.7 136 5.5 84.6 2.2
PEtPh2 4.9 2066.7 140 8.8 71.7 4.3
PPh3 2.7 2068.9 145 14.1 62.4 11.7

Phosphine modified cobalt hydroformylation is only used by Shell. It is

tightly coupled to Shell's Higher Olefins Process (SHOP) that produces a C4
through C20 blend of linear, internal alkenes for hydroformylation to detergent
grade alcohols. Exact details of Shell's commercial process have never been
published. For example, the specific trialkylphosphine used is not widely known
outside of Shell. They do NOT use PBu3 as it is too volatile.
 Sabhuku Mudavanhu
Hydroformylation 11

Rhodium Phosphine Catalysts. In 1965 Osborn, Young and

Wilkinson reported that Rh(I)-PPh3 complexes were active and highly
regioselective hydroformylation catalysts for 1-alkenes, even at ambient
conditions. Although Slaugh and Mullineaux had filed a patent in 1961
that mentioned Rh/phosphine combinations for hydroformylation, it was
Wilkinson's work that really ignited serious interest in rhodium
phosphine hydroformylation catalysts. The initial catalyst system was
derived from Wilkinson's catalyst, RhCl(PPh3)3, but it was rapidly
discovered that halides were inhibitors for hydroformylation. It was
best, therefore, to start with halide-free rhodium starting complexes.
HRh(CO)(PPh3)3 and Rh(acac)(CO)2 (acac = acetoacetonate) are two
commonly used starting materials for hydroformylation. The currently
accepted mechanism for Rh/PPh3 hydroformylation is shown below.
The steps are directly analogous to Heck's mechanism for HCo(CO)4.
Rh/PPh3 Hydroformylation Cycle
H R H
- CO + alkene
PPh3 OC PPh3 PPh3
OC Rh Rh Rh
PPh3 Ph3P H PPh3
C + CO C
O O
O

H R
H
H PPh3 OC PPh3
Rh Rh
Ph3P Ph3P
C
R R
O
O
+ CO

+ H2
O R R
- CO
PPh3 OC PPh3 PPh3
OC Rh Rh OC Rh
PPh3 Ph3P PPh3
C + CO R C
O O O

Wilkinson noted that HRh(CO)(PPh3)2 was very selective to

aldehyde products (no alcohol formation, no alkene hydrogenation or
 Sabhuku Mudavanhu
Hydroformylation 12

isomerization) and that very high linear to branched aldehyde

selectivities of 20:1 for a variety of 1-alkenes could be obtained under
ambient conditions (25° C, 1 bar 1:1 H2/CO). At higher temperatures,
the rate increased, but the regioselectivity dropped (9:1 at 50° C).
Running under 80-100 bars of H2/CO decreased the linear to branched
aldehyde selectivity to only 3:1.
Pruett (at Union Carbide) quickly provided the next critical discovery
that, along with the work of Booth and coworkers at Union Oil, allowed
commercialization of the HRh(CO)(PPh3)2 technology. They found
that the use of rhodium with excess phosphine ligand created an active,
selective, and stable catalyst system at 80-100 psig and 90° C.10 Union
Carbide, in conjunction with Davy Powergas and Johnson Matthey,
subsequently developed the first commercial hydroformylation process
using rhodium and excess PPh3 in the early 1970's. The need for excess
phosphine arises from the facile Rh-PPh3 dissociation equilibrium
shown below. Loss of PPh3 from HRh(CO)(PPh3)2 generates
considerably more active, but less regioselective hydroformylation
catalysts. The addition of excess phosphine ligand shifts the phosphine
dissociation equilibrium back towards the more selective
HRh(CO)(PPh3)2 catalyst. This explains why higher CO partial
pressures lower the product regioselectivity, in marked contrast to what
is observed for HCo(CO)4-catalyzed hydroformylation.

+CO +CO +CO CO

PPh3 PPh3 CO
-PPh3 -PPh3 -PPh3
Ph3P Rh H OC Rh H OC Rh H OC Rh H
+PPh3 +PPh3 +PPh3
PPh3 PPh3 PPh3 CO
-CO -CO -CO
active, but not highly active,
Inactive Selective Catalyst not selective
very selective
 Sabhuku Mudavanhu
Hydroformylation 13

The regioselectivity of HRh(CO)(PPh3)2 is strongly related to the

concentration of PPh3 in solution (up to a certain point) and the H2/CO
ratio used. Commercial hydroformylation reactions are run using
solutions that have PPh3 concentrations of 0.3 M or higher (typical Rh
concentration around 1 mM). This corresponds to PPh3 weight
percentages of 8-50% of the total solution in commerical reactors. The
effect of PPh3 concentration on the rate and selectivity for the
hydroformylation of 1-hexene can be seen in Table 2.
Table 2. Rate constants and Regioselectivities for the Hydroformylation of 1-
Hexene using Rh(acac)(CO)2 with Different PPh3 Concentrations. Reaction
Conditions: 90 psig (6.2 bar), 1:1 H2/CO, 90° C.

[Rh] [PPh3] PPh3/Rh kobs l:b

(mM) (M) ratio (min mM Rh-1)
-1 ratio

0.5 0.41 820 0.032 11

1 0.82 820 0.016 17

Note that doubling the PPh3 concentration cuts the rate constant in
half, even though the rhodium concentration was also doubled! The
selectivity, on the other hand, increases to 17:1 for the C7 aldehyde
linear to branched ratio. The "ultimate" experiment of running
HRh(CO)(PPh3)2 in molten PPh3 has been done with propylene giving
a 16:1 linear to branched aldehyde ratio. Commercially, propylene is
run with PPh3 concentrations around 0.4 M with a catalyst
concentration of about 1 mM (400 fold excess of PPh3), which gives a
linear to branched selectivity of ~8-9:1. Lower CO partial pressures
also would be expected to favor higher regioselectivities, and this is
indeed the case. Rh/PPh3 reactions are often run with an excess of
hydrogen (2:1 H2/CO ratios are common). Too high a hydrogen partial
pressure, or too low a CO partial pressure, however, will increase the
alkene hydrogenation and isomerization side reactions to an
unacceptable level.
 Sabhuku Mudavanhu
Hydroformylation 14

The rate determining step in Rh/PPh3 not fully understood. It was assumed
early on in analogy to the HCo(CO)4 catalyst system, that the rate determining
step was H2 addition to the Rh(I)-acyl species. This has been disputed by several
authors in more recent studies. Kastrup and coworkers concluded from 31P NMR
studies that the rate determining step could be the initial coordination of alkene to
the HRh(CO)(PPh3)2 catalyst species.11 Moser and coworkers, in a similar vein,
proposed that the rate determining step is CO dissociation from
HRh(CO)2(PPh3)2 to once again generate the 16e species HRh(CO)(PPh3)2.12
Combining both of these proposals, Unruh concluded that several of the
fundamental steps in Rh/PPh3 hydroformylation appear to have similar rate
constants, making it difficult to specify one overall rate determining step, as they
may probably vary with the exact reaction conditions. The complexity of the
phosphine/CO ligand dissociation/association processes and the many
catalytically active rhodium complexes present was most clearly pointed out by
Tolman and Faller who presented a 3-dimensional mechanistic scheme for the
hydroformylation of alkenes by Rh/PPh3 complexes.13 The mechanism shown
here only indicates the core catalytic cycle that is believed to give the highest
product aldehyde regioselectivity.
The other important reason for adding excess phosphine ligand is to
minimize ligand fragmentation reactions that lead to catalyst
deactivation. If a 14e, highly unsaturated species such as
HRh(CO)(PPh3) is formed the very electrophillic metal center can
attack the PPh3 ligand (either intra- or intermolecularly). This leads to
cleavage of the P-Ph bond and formation of either alkyldiphenyl
phosphines or, in the worst case, phosphide-bridged dimers which are
inactive for hydroformylation:
Ph Ph
Ph
Ph
+ H2 P
P
Rh Rh
- benzene P
Rh Rh

Ph Ph
 Sabhuku Mudavanhu
Hydroformylation 15

This fragmentation process has been studied and proceeds by oxidative

addition of the P-Ph bond to an unsaturated Rh center.14,15 A separate PPh3
activation process involving ortho-metallation of the phenyl group can also occur.
Triarylphosphine ligands and phosphite ligands are particularly susceptible to this
fragmentation because of the availability of - or lone-pair electron density on the
ligands that can interact with an empty Rh orbital. The fact that they are
moderate to poor electron-donating ligands also enhances the electrophillicity of
the rhodium center.16 Trialkylphosphine ligands should be relatively inert to
these types of Rh-induced fragmentations due to the lack of any -electron
density on the ligand. The considerably stronger -donation ability of alkylated
phosphines also works to decrease the electrophillicity of the rhodium center.
Unfortunately, trialkylphosphine ligands usually dramatically lower both the rate
and selectivity of rhodium hydroformylation catalysts.

Chelating phosphines have interesting effects on hydroformylation.

R2P(CH2)xPR2 (x = 2-4) ligands with alkyl or aryl substituents
generally form terrible catalysts that give poor rates and selectivities, as
well as extensive alkene isomerization and hydrogenation side reactions.
Tridentate tripodal phosphine ligands, such as MeC(CH2PPh2)3, also
generate catalysts with very poor rates and regioselectivities.17 High
pressure NMR studies have shown that an arm-on, arm-off equilibrium
is operational to generate the active unsaturated 16e- catalyst species
HRh(CO)(2-MeC(CH2PPh2)3).18
Matsumoto and Tamura (at Kuraray Co.) have demonstrated that the
combination of simple bis(diphenylphosphino)alkane ligands and PPh3
can have a very positive effect on catalyst stability and the reduction of
unwanted side reactions.19 This is most evident in the hydroformylation
of a reactive alkene such as allyl alcohol. The use of HRh(CO)(PPh3)2
in the presence of excess PPh3 leads to relatively rapid catalyst
deactivation to unidentified species. The addition of just over 1
equivalent of Ph2PCH2CH2CH2CH2PPh2 (dppb) leads to a stable,
active hydroformylation catalyst.20 Use of dppb either by itself, or in
quantities higher than 2 equivalents, leads to catalyst deactivation and/or
poor activities and selectivities. ARCO Chemical licensed the Kuraray
 Sabhuku Mudavanhu
Hydroformylation 16

technology to build the first plant in 1990 for the hydroformylation of

allyl alcohol to produce 1,4-butanediol:

O
H 2 /CO
OH OH
H

allyl alchol

H2
OH
HO
1,4-butanediol

It is not exactly understood how10the mixed ligand Rh/dppb/PPh3

Scheme
catalyst system functions. Matsumoto proposed that the arm-on, arm-
off equilibrium shown below is operational. A species such as (2)
would function much like a normal HRh(CO)(PPh3)2 catalyst, but the
ability to reform the chelate to form a slightly more electron-rich
complex (3) would tend to inhibit alkene isomerization and/or
degradation reactions which require 16e- unsaturated species.

H H
P
P P Rh PPh3 P Rh PPh3
C C
O O

(2) (3)
Scheme 11
 Sabhuku Mudavanhu
Hydroformylation 17

Aqueous-Phase Rh Hydroformylation
One important variant of Rh/PPh3 catalysis is the water-soluble
catalyst system developed by Emile Kuntz at Rhone-Poulenc in 1981.
By using a sulfonated PPh3 ligand, P(Ph-m-SO3 Na+)3 (TPPTS), a
highly water soluble catalyst is generated: HRh(CO)[P(Ph-m-SO3
Na+)3]3. In aqueous solution
the catalyst essentially has a 9 TPPTS SO3 Na

charge, making it totally P

insoluble in all but the most Na O3S
polar organic solvents. Excess
phosphine ligand is required for
good L:B selectivities, as with
conventional Rh/PPh3 catalysts,
but lower concentrations are Na O3S
required because the TPPTS
phosphine dissociation equilibrium in water is shifted towards the Rh-
phosphine coordinated complexes.
Shorter chain alkenes (C2-C4) are water soluble enough that
migration into the aqueous catalyst phase occurs to allow
hydroformylation. Remigration of the aldehyde product back into the
more soluble organic phase allows easy separation of product from
catalyst. Rather high linear to branched regioselectivities of 16-18:1 for
propylene can be obtained via this water soluble catalyst. Rates are
slower than with conventional Rh/PPh3 catalysts due to lower alkene
concentrations in the water phase and higher amounts of the inactive
tris-phosphine Rh complex. The process is limited to the shorter chain
alkenes that have some appreciable water solubility. Alkenes higher
than 1-pentene are not soluble enough in water. Celanese-Ruhrchemie
currently operates several hydroformylation plants based on this water
soluble rhodium catalyst technology.
 Sabhuku Mudavanhu
Hydroformylation 18

2-ethyl-1-hexanol Product
Rh/PPh3 catalyzed hydroformylation is responsible for just over 50%
of all oxo alcohols produced. Propylene is the largest single alkene
hydroformylated to produce butylaldehyde, which can be hydrogenated
to produce butanol, or dimerized by an aldol condensation and then
hydrogenated to form 2-ethyl-1-hexanol (2EH), the largest single
product produced by hydroformylation (over 5 billion lbs a year). 2-
ethyl-1-hexanol is usually reacted with phthalic anhydride to produce
dialkyl phthalic esters that are used as plasticizers to keep polyvinyl
chloride plastics soft and flexible.
2-ethyl-hexanol
O OH O O H2
(2EH)
-H2O
2 Et Et Et Et
H H H OH
aldol Et Et Et
condensation

New Generation Rh Catalysts. Union Carbide (now Dow), Eastman

Chemical, and Prof. Piet van Leeuwen (University of Amsterdam) have
independently developed a new generation of chelating bisphosphine
rhodium catalysts that show remarkably high product regioselectivities
and good to high activities.
Two of the best Eastman bisphosphine ligands, developed by Devon,
Phillips, Puckette and coworkers are called BISBI and BISBI* that form
9-membered chelate rings with the Rh center. Rh catalysts based on
these phosphines are highly regioselective, giving linear to branched
(L:B) aldehyde product ratios for propylene of > 30:1 (commercial
Rh/PPh3 catalysts give around an 8:1 ratio) with rates about twice that
of Rh/PPh3.
 Sabhuku Mudavanhu
Hydroformylation 19

PPh2 PPh2 PPh2

PPh2 PPh2 PPh2

Bisbi Bisbi* Naphos

O O
O P P O
O O
O
PPh2 PPh2

UC-44 Xantphos

A closely related bisphosphine ligand used by Herrmann and Beller

(independently) for hydroformylation studies is Naphos (not to be
confused with the Binap bisphosphine ligand that has the PPh2 groups
directly bonded to the naphthalene rings).
Prof. Piet van Leeuwen at the University of Amsterdam developed
the Xantphos family of ligands that also show high L:B regio-
selectivities and activities similar to that of Rh/PPh3. Some catalytic
comparisons between Rh/PPh3, Bisbi, Naphos and Xantphos for the
hydroformylation of 1-hexene are shown below (90ºC, 6.2 bar 1:1
H2/CO, 1000 eq. 1-hexene, acetone solvent, iso = isomerization):
Catalyst (1 mM) Init TOF (min1) Aldehyde L:B % iso
Rh/PPh3 (1:400) 13(1) 9:1 < 0.5
Rh/Bisbi (1:5) 25(2) 70:1 < 0.5
Rh/Naphos (1:5) 27(1) 120:1 1.5
Rh/Xantphos (1:5) 13(2) 80:1 5.0
 Sabhuku Mudavanhu
Hydroformylation 20

The Union Carbide (now Dow) ligand system, UC-44, developed by

Billig and co-workers is a bulky bisphosphite ligand that also forms a 9-
membered chelate ring to the rhodium center. This generates a highly
regioselective hydroformylation catalyst that, like BISBI/Naphos, has
linear to branched aldehyde product ratios for the hydroformylation of
propylene of well over 30:1. Due to the presence of the poorly -
donating phosphite ligands, however, the rhodium center is highly
active, giving hydroformylation rates for 1-alkenes that are about 5
times faster than Rh/PPh3 catalysts. Indeed, the catalyst is active
enough and a good enough isomerization catalyst to give high linear
regioselectivities for the hydroformylation of some internal alkenes,
particularly, 2-butene (25:1 linear to branched aldehyde ratio). This
could form the basis of a new fourth generation hydroformylation
technology.
Rh-induced ligand fragmentation problems, however, may well limit
the commercialization of these active and selective catalyst systems.
Phosphite ligands, in particular, are sensitive to Rh-induced and organic
cleavage reactions.
Casey and van Leeuwen have proposed and presented good evidence
that part of the regioselectivity in rhodium bisphosphine catalysts is
related to the ability of the chelating phosphine to favor an equatorially
chelated trigonal bipyramidal structure, i.e., maintain a metal chelate
bite angle around 120°. This is refered to as the “Bite Angle
Hypothesis.” All the new generation bulky chelating ligands are indeed
capable of doing this, while “normal” chelating ligands, such as
bis(diphenylphosphino)ethane (dppe), cannot and give very poor
selectivities.
 Sabhuku Mudavanhu
Hydroformylation 21

Bimetallic Hydroformylation
A unique bimetallic rhodium complex that provides a very strong
example of bimetallic cooperativity in homogeneous catalysis has been
reported by Stanley and coworkers.21 They designed a novel
binucleating tetraphosphine ligand (racemic- and meso-et,ph-P4) that
can both bridge and chelate two transition metal centers, producing
bimetallic complexes that only have a single, conformationally flexible
bridging group.

P PEt2 P
Ph
P Ph P Ph
Ph PEt2
Et2P Et2P

racemic-et,ph-P4 meso-et,ph-P4

[Rac-Rh2(nbd)2(et,ph-P4)](BF4)2 (nbd = norbornadiene) is a

catalyst precursor to a highly active and regioselective hydroformylation
catalyst for 1-alkenes under mild conditions (the meso-Rh2 complex is
far less active and has much higher side reactions). A comparison
between [rac-Rh2(nbd)2(et,ph-P4)](BF4)2 and some of the best
monometallic catalysts is shown in the table below (90ºC, 6.2 bar 1:1
H2/CO, 1000 eq. 1-hexene, acetone solvent). It was also discovered that
adding 30% water to the acetone solvent dramatically reduces catalyst
degradation rxns, increasing both the rate and selectivity.22
Catalyst (1 mM) Init TOF (min1) Aldehyde L:B % iso
[rac-Rh2P4]2+ 20(1) 25:1 2.5
[rac-Rh2P4]2+ (30% H2O) 30(1) 33:1 < 0.5
Rh/PPh3 (1:400) 13(1) 9:1 < 0.5
Rh/Bisbi (1:5) 25(2) 70:1 < 0.5
Rh/Naphos (1:5) 27(1) 120:1 1.5
Rh/Xantphos (1:5) 13(2) 80:1 5.0
 Sabhuku Mudavanhu
Hydroformylation 22

Since the racemic-Rh2(nbd)2(et,ph-P4)2+ precursor complex does

not have a Rh-Rh bond it was straight forward to prepare mono- and
bimetallic model systems to test whether the two metal centers were
working independently or if the complex was fragmenting to generate
active monometallic species. The hydroformylation activity of a series
of monometallic complexes and spaced bimetallic complexes (shown
below) were studied. These were all found to be terrible hydro-
formylation catalysts, giving extremely poor rates and selectivities.
2+

Rh Rh Ph Rh

R2P PR2 R 2P P P PR2

Ph

2+

Rh Ph Rh
R2 P P P PR2

Ph

This led to the initial proposal of a bimetallic cooperativity

mechanism involving neutral bimetallic complexes. When one started
with a neutral bimetallic complex like rac-Rh2(3-allyl)2(et,ph-P4) a
very poor hydroformylation catalyst formed. Subsequent in situ FT-IR
spectroscopic studies on racemic-Rh2(nbd)2(et,ph-P4)2+ and racemic-
Rh2(3-allyl)2(et,ph-P4) under H2/CO pressure and catalytic conditions
clearly revealed that the active bimetallic catalyst complex has high
frequency terminal CO stretching frequencies, leading to the conclusion
that it is a dicationic hydrido-carbonyl complex.23 Furthermore, the
catalyst activity appears to track with the intensity of the bridging CO
bands around 1835 cm-1, leading the the following proposed active
catalyst structure.
 Sabhuku Mudavanhu
Hydroformylation 23

Catalyst Precursor

1794 Et2P PEt2

2:1 L:B
35 TO/hr Rh Rh
1895 P P
1970
Ph
Ph
1929

2076 Et2P PEt2 2+

25:1 L:B Rh Rh
1832
1200 TO/hr P P
Ph
2096 Ph
2038

2100 2000 1900 1800

Wavenumbers (cm -1)

Proposed active dirhodium catalyst:

H H 2+
O
C PEt2
Rh Rh
Et2P C
O
Ph P P
Ph
There is a facile terminal CO addition-dissociation equilibrium on the
species above (each Rh is 16e-) to generate complexes with one or two
additional terminal CO ligands.

Problem: Why is the dicationic charge so important on this

catalyst?
 Sabhuku Mudavanhu
Hydroformylation 24

The proposed mechanism for this dicationic bimetallic catalyst is

shown below:
O O
C 2+ + H2 C 2+
OC  CO OC
Rh Rh
Ph PEt2 Ph
PEt2
Et2P CO Et2P CO
P P P P CO
Ph Rh Ph Rh
CO H
C H
3 O A

+ CO  CO

O O O
C C 2+
2+ + H2 C H
O
C PEt2  CO H PEt2
Rh Rh Rh Rh
Et2P C Et2P C
O O
Ph P P Ph P P
Ph Ph

4 O 2*
+ 2CO
R H

R O
H 2+ H H 2+
O O
C C PEt2
PEt2 Rh Rh
Rh Rh
Et2P C Et2P C
O O
Ph P P Ph P P
Ph Ph
D
2
R

H 2+ R 2+
H H
O O
OC C PEt2 + CO C PEt2
Rh Rh Rh Rh
Et2P C Et2P C
O O
Ph P P Ph P P
Ph Ph
C B
 Sabhuku Mudavanhu
Hydroformylation 25

References:
1) D. S. Breslow and R. F. Heck, Chem. Ind. (London), 1960, 467.
2) R. F. Heck and D. S. Breslow, J. Am. Chem. Soc., 1961, 83, 4023.
3) R. Wyman, J. Organomet. Chem., 1974, 66, C23.
4) M. F. Mirbach, J. Organomet. Chem., 1984, 265, 205.
5) W. R. Moser, in 'ACS Advances in Chemistry Series', eds. W. R. Moser and D. W. Slocum, ACS,
Washington, D.C., 1992, Vol. 230, Chapter 1, p. 14.
6) B. Fell, W. Rupilius, and F. Asinger, Tetrahedron Lett., 1968, 3261.
7) M. Bianchi, F. Paicenti, P. Frediani, and U. Matteoli, J. Organomet. Chem., 1977, 137, 361.
8) B. L. Haymore, A. van Asselt, and G. R. Beck, Ann. New York Acad. Sci., 1984, 415, 159.
9) L. H. Slaugh and R. D. Mullineaux, J. Organometal. Chem., 1968, 13, 469.
10) R. L Pruett and J. A. Smith, J. Org. Chem., 1969, 34, 327.
11) R. V. Kastrup, J. S. Merola, A. A. Oswald, in 'ACS Advances in Chemistry Series', eds. E. L. Alyea and
D. W. Meek, ACS, Washington, D.C., 1982, Vol. 196, Chapter 3, p. 43.
12) W. R. Moser, C. J. Papile, D. A. Brannon, R. A. Duwell, and S. J. Weininger, J. Mol. Catal., 1987, 41,
271.
13) C. A. Tolman and J. W. Faller, in 'Homogeneous Catalysis with Metal Phosphine Complexes', ed. L. H.
Pignolet, Plenum, New York, 1983, Chapter 2, p. 93.
14) A. G. Abatjoglou, E. Billig, and D. R. Bryant, Organometallics, 1984, 3, 923.
15) M. Lewin, Z. Aizenshtat, and J. Blum, J. Organomet. Chem., 1980, 184, 255.
16) W. R. Moser, C. J. Papile, and S. J. Weininger, J. Mol. Catal., 1987, 41, 293.
17) C. Bianchini, A. Meli, M. Peruzzini, and F. Vizza, Organometallics, 1990, 9, 226.
18) G. Kiss and I. Horváth, Organometallics, 1991, 10, 3798.
19) M. Matsumoto and M. Tamura, J. Mol. Catal., 1982, 16, 209.
20) M. Matsumoto and M. Tamura, J. Mol. Catal., 1982, 16, 195.
21) M. E. Broussard, B. Juma, S. G. Train, W.- J. Peng, S. A. Laneman and G. G. Stanley, Science, 1993,
260, 1784.
22) D. A. Aubry, N. N. Bridges, K. Ezell, and G. G. Stanley, J. Am. Chem. Soc., 2003, 125, 11180.
23) R. C. Matthews, D. K. Howell, W.-J. Peng, S. G. Train, D. W. Treleaven, G. G. Stanley, Angew. Chem.
Int. Ed., 1996, 35, 2253.
 Sabhuku Mudavanhu

Monsanto (BP) Acetic Acid & Related Processes

The carbonylation of methanol produces acetic acid:

O
H3C OH + CO
H3C OH
This is the second largest industrial homogeneous carbonylation process
with over 7 billion pounds of acetic acid produced each year using this
technology. Prior to 1970, acetic acid was made using cobalt catalysts
(BASF process) requiring rather severe conditions. In 1970 Monsanto
commercialized a rhodium carbonyl iodide catalyst that is commonly
called the Monsanto Acetic Acid Process (developed in the late 60’s by
James Roth and his research team at the corporate research center in St.
Louis). In 1986 Monsanto sold the acetic acid plant and technology to
British Petroleum (BP), but it is still commonly referred to as the
Monsanto Acetic Acid process.
As with hydroformylation catalysis, rhodium is 103 to 104 times more
active than the corresponding cobalt catalyst, which means that much
lower CO pressures and moderately lower temperatures are required.
Most importantly, the rhodium catalyst gives extremely high
selectivities to acetic acid:
Cobalt Rhodium
Concentration ~ 101 M ~ 103 M
Temperature ~ 230° C ~180° C
Pressure 500-700 atm 30-40 atm
Selectivity 90% > 99%
H2 effect CH4, CH3CHO, no adverse
EtOH byproducts effect
 Sabhuku Mudavanhu
Acetic Acid 2
The mechanism has been extensively studied by Forster and coworkers
at Monsanto and is shown below. This catalytic reaction is an unusual
dual cycle system involving HI as one catalyst and [RhI2(CO)2] as the
transition metal component. HI catalyzes the conversion of MeOH to
MeI and H2O at the beginning of the Rh-catalyzed carbonylation
reaction, followed by regeneration of HI at the end of the Rh-cycle by
hydrolysis of the acyl-iodide. The Rh catalyst carbonylates the MeI to
produce the acyl-iodide.

O + HI
CH3OH HI
H3C OH
+ H2O
CH3
CH3I
OC CO OC CO
+ H2O Rh Rh
I I I I
I
O

H3C I

CO O O
OC + CO OC
Rh CH3 Rh CH3
I I I I
I I

The reaction is independent of CO pressure, and first order in both

rhodium and MeI. The rate determining step is the oxidative addition of
MeI to the [Rh(CO)2I2] catalyst. Thus, the production of MeI from
methanol, catalyzed by HI, is critically important. Iodide ligands are
considered to be quite important in this reaction due to the HI catalyzed
conversion of MeOH to MeI and their relatively good donor abilities on
the Rh center. The negative charge on the [Rh(CO)2I2] catalyst is
believed to be critical in assisting the oxidative addition of MeI to the
rhodium center. The alkyl species, [Rh(CO)2(Me)I3], is extremely
reactive towards CO insertion to form the acyl complex.
 Sabhuku Mudavanhu
Acetic Acid 3
Celanese LiI Modified “Low Water” Catalyst System
One problem with the original Monsanto process is that moderately high
amounts of H2O are needed to produce H2 in the reactor via the water-
gas shift rxn (CO + H2O CO2 + H2). The water and H2 were
needed to react with precipitated RhI3 and “inactive” [RhI4(CO)2],
which formed from side reactions, to regenerate the active Rh(I)
catalyst. The reaction of water with inactive [RhI4(CO)2] to generate
active Rh(I) catalyst, [RhI2(CO)2], is shown below.
H H
O H H
O 2- O
I - H+ I - I-
OC I O I O I
Rh Rh Rh
OC I OC I OC I
I I I

- CO2

- HI H
I I I
Rh Rh
OC CO + CO OC I
I

The relatively high amounts of H2O needed also increases the amount of
the highly corrosive HI present leading to engineering problems. The
water reactivation process is also not especially efficient leading to more
inactive Rh present in the reactor.
In the late 70’s Celanese developed a major improvement on the
Monsanto technology not covered by their narrow patent that involved
the simple addition of LiI (and other proprietary modifiers) to reduce the
amount of H2O (and HI) used in the catalysis. Added LiI increased the
catalyst stability by minimizing the side reactions that produced inactive
Rh(III) species. It also increased the amount of the more reactive
dianionic [RhI3(CO)2]2 catalyst species. This considerably increased
the catalyst activity, throughput, and efficiency.
 Sabhuku Mudavanhu
Acetic Acid 4
Problem: Increasing the iodide concentration increases the amount
of the following 18e- complex. Why is this more reactive and why
doesn’t this saturated 18e- complex slow down the subsequent
oxidative addition reaction with MeI?

I 2- I

+ I-
OC I
OC
Rh
I
+ CH3I Rh
OC I OC I
CH3

BP Ir-Based Cativa System

The Cativa Ir-based acetic acid catalyst system was announced with
much fanfare in 1999. However, much of this catalytic chemistry was
part of the original Monsanto Acetic Acid patent. The Ir cycle was
originally studied in considerable detail by Forster (along with the Rh
system) in 1979 (JCS Dalton, 1979, 1639). The fundamental
mechanism is essentially the same as the Rh cycle:

O + HI
CH3OH HI
H3C OH
+ H2O
CH3
CH3I
OC CO OC CO
+ H2O Ir Ir
I I I I
I
O

H3C I

CO O O
OC + CO OC
Ir CH3 Ir CH3
I I I I
I I
 Sabhuku Mudavanhu
Acetic Acid 5

The main differences between the Ir and Rh catalyst systems:

1) The rate determining step for Ir is the migratory insertion of the Ir-
CH3 and Ir-CO ligands. The MeI oxidative addition step is faster
for Ir due to its lower electronegativity.
2) The stronger Ir-ligand bonds slow down the migratory insertion step
and reductive elimination steps (Foster noted this in 1979 paper).
3) There are considerably fewer side reactions in the Ir system to make
inactive M(III) complexes (soluble or insoluble). This is also tied
into point #2.
This enables the use of low water conditions that makes the BP Ir
system competitive with the Celanese LiI modified low water high-
activity Rh catalyst. Due to patents issued by Celanese and Eastman
(see next section), BP could not make use of “normal” additives to
convert the Rh catalyst to a low water system.
BP found, however, that a modifier was needed to remove an iodide
ligand to generate less electron-rich (more unsaturated) complexes that
would favor the CO-methyl migratory insertion and the final reductive
elimination of acyl-iodide. They Acetic Acid Catalyst Studies
found that added RuI2(CO)3 would 40 Ir-Ru 1:2 ratio
Ir
reversibly abstract an iodide ligand Rh (no modifiers)

from the [IrI3(CH3)(CO)2] 30

Rate M/hr

complex to enhance the rate of the

20
CO-methyl migratory insertion.
The enhancing effect is shown in 10
the graph to the right.
(Haynes, JACS, 2004, 126, 2847) 0
0 5 10 15 20
Water conc % (w/w)
 Sabhuku Mudavanhu
Acetic Acid 6

Eastman Chemical Acetic Anhydride Process

A very closely related process is the Eastman Chemical carbonylation of
methyl acetate to produce acetic anhydride. This was commercialized
in 1983 and produces over 800 million pounds of acetic anhydride a
year at their Kingston, TN plant.

O
O O + I- O
H3C OCH3
H3C O CH3 H3C O
+ I-
CH3
O CH3I
OC CO OC CO
Rh Rh
H 3C O I I I I
I
O

H3C I

CO O O
OC + CO OC
Rh CH3 Rh CH3
I I I I
I I

Note that this is essentially the same as the Monsanto/Celanese

processes, only the initial reactant has changed. Eastman also worked
out that adding excess Li(acetate), much like Celanese adds LiI,
eliminates the need for water completely, which is important if one
wants to make water sensitive acetic anhydride.
Since this wasn’t covered by the Monsanto (or Celanese) patents,
Eastman Chemical didn’t have to pay any royalty or licensing fee,
saving them a bunch of $$.
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 1

Coupling Reactions
Organometallic chemistry has provided important new methods to carry out
carbon-carbon or carbon-heteroatom bond formation. Such processes, termed
coupling reactions, now have a central place in organic synthesis. The most
important ones are summarized below. They often bear the name of their
discoverer (organic tradition).
Stille coupling:
organotin
Pd(0)
R-X + R'-SnR3 R-R' + XSnR3
aryl or
vinyl halide

Negishi coupling:
organozinc
Pd(0)
R-X + R'-ZnR R-R' + XZnR
aryl or
vinyl halide
Suzuki coupling:
organoboron
Pd(0)
R-X + R'-B(OH)2 R-R' + XB(OH)2
aryl or
vinyl halide
Heck reaction:
alkene
Pd(0) R
R-X + + HX
R'
aryl or R'
vinyl halide
Sonogashira coupling:
alkyne
Pd(0)
R-X + R' R R' + HX
aryl or
vinyl halide
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 2

Cross-Coupling of Organometallics and Halides

Pd(0)
R-X + R'-M R-R' + MX
M = MgX, ZrCp2Cl, ZnX, SnR3, B(OR)2, AlMe2, SiR3, Cu,…

The mechanism involves oxidative addition of the halide or triflate to the

initial Pd(0) phosphine complex to form a Pd(II) species. The key slow step
is a transmetallation, so called because the nucleophile (R') is transferred
from the metal in the organometallic reagent to the palladium and the
counterion (X = halide or triflate) moves in the opposite direction. The new
Pd(II) complex with two organic ligands undergoes reductive elimination to
give the coupled product and the Pd(0) catalyst ready for another cycle.
L Pd L
R'-R
+ R-X

L R L R
Pd Pd
L R' L X

M-X R'-M
transmetallation
The halide partner (R–X) must be chosen with care, as -hydride elimination
would decompose the first intermediate during the slow transmetallation step.
The choice for R is restricted to substituents without -hydrogen atoms:
vinyl, allyl, benzyl, and polyfluoroalkyl halides, triflates, and phosphates
have all been coupled successfully.
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 3

The organometallic reagent (R'–M) can be based on Mg, Zn, Cu, Sn, Si, Zr,
Al, or B and the organic fragment can have a wide variety of structures as
coupling is faster than -hydride elimination.

Formation of the active species may conveniently be carried out in situ by

reduction of a Pd(II) precursor, for example, PdCl2, Pd(OAc)2, or Na2PdCl4.
The reduction of Pd(II) to Pd(0) can be achieved with amines, phosphines,
alkenes, and organometallics such as DIBAL-H, butyl lithium, or
trialkylaluminium.

Reduction with Et3N:

ligand H -hydride reductive
exchange PdL2X X elimination elimination
PdL2X2 N HPdL2X PdL2 + HX
Et2
- NEt2 X

Reduction with PPh3:

ligand Ph3P PPh3 reductive
exchange PdOAc elimination
Pd(OAc)2 O Pd Pd-PPh3
Ph3P AcO P OAc
Ph3 + Ac2O
OAc O
+ Ph3PO

Reduction with ethylene:

migratory -hydride reductive
H
insertion elimination elimination
PdL2X2 X PdL2X HPdL2X PdL2 + HX
- X

Reduction with an organometallic:

reductive
2 R-M R elimination
PdL2X2 PdL2 + 2 MX PdL2 + R-R
R

Usually, a stoichiometric excess of an amine such as Et3N is part of the

reaction mixture, serving both as a base to trap the HX formed and as a
reducing agent for Pd.
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 4

Stille Coupling
The Stille coupling uses organotin compounds (called stannanes) as
organometallic components. Since its first reported use in the late 1970's, the
reaction has been widely used for the coupling of both aromatic and vinylic
systems. The Stille coupling represents over half of all current cross-coupling
reactions, however, due to their high toxicity, stannanes tend to be replaced
more and more with organozinc and organoboron compounds.
The reaction may be carried out intramolecularly and with alkynyl stannanes
instead of the more usual aryl or vinyl stannanes to form medium-sized rings.
For example, the reaction below forms a 10-membered ring containing two
alkynes.

Suzuki Coupling
Since first being published in 1979, the Suzuki coupling of a boronic acid
with a halide or triflate has developed into one of the most important cross-
coupling reactions, totalling about a quarter of all current palladium-catalysed
cross-coupling reactions.
As in the Stille coupling, the geometry of unsaturated components is
preserved during the coupling, so this is an excellent method for
stereospecific diene synthesis. For example, coupling of an E-vinyl boronic
acid with a Z-vinyl bromide in toluene in the presence of Pd(0) with
potassium hydroxide as the base gave the corresponding E,Z-diene in good
yield.
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 5

The mechanism of the Suzuki reaction proceeds by oxidative addition of the

vinylic or aromatic halide to the Pd(0) complex and generates a Pd(II)
intermediate. This intermediates undergoes a transmetallation with the
alkenyl boronate, from which the product is expelled by reductive
elimination, regenerating the Pd(0) catalyst. One difference between the
Suzuki and Stille couplings is that the boronic acid must be activated, usually
with a base such as sodium or potassium ethoxide or hydroxide. The base
converts the borane (BR3) into more a reactive boronate (BR3(OH)–).
Activation of the boron atom enhances the polarization of the organic ligand
and facilitates the transmetallation step.

L Pd L
R'-R
+ R-X

L R L R
Pd Pd
L R' L X

B(OH)3X R'-B(OH)3
transmetallation

R'-B(OH)2 + NaOH
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 6

Heck Reaction
The Heck reaction is a powerful and efficient method for C–C bond
formation in which haloarenes and haloalkenes (or triflates) couple with
alkenes in the presence of a Pd(0) catalyst to form a new alkene. The process
is often stereo- and regioselective.
alkene
Pd(0) R
R-X + + Base-HX
R' Base
aryl or R'
vinyl halide

- R can be an aryl, vinyl, benzyl or allyl group (in other words, any group
without -hydrogens on a sp3 carbon atom).
- X can be a halide (Cl, Br, or I) or triflate (OSO2CF3).
- The alkene can be mono- or disubstituted and can be electron-rich, -poor,
or neutral.
- The base does not have to be strong. Et3N, NaOAc, or aqueous Na2CO3 are
often used. The base is, however, stoichiometric and one equivalent of
base is generated for each equivalent of product.
- The catalyst is a Pd(0) complex either preformed or generated in situ from
stable Pd(II) precursors.

The rate of reaction and regioselectivity are sensitive to steric hindrance

about the C=C bond of the vinylic partner. For simple aryl halides reacting
with alkenes, the rate of reaction as a function of alkene substitution varies
according to the following sequence:
CH2=CH2 > CH2=CH-OAc > CH2=CH-Me > CH2=CH-Ph > CH2=C(Me)Ph
krel: 14,000 970 220 42 1

The regioselectivity of addition is given below for a number of alkenes.

Although electronic effects may play a small role in directing attack by the
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 7

metal in the insertion step, steric effects seem to be the dominant factor by
far.
CO2Me CN Ph 20

100 0 100 0 100 0 80

HO
99 CO2Me Ph 79 Ph

1 100 21 90 10

The mechanism involves the oxidative addition of the halide, insertion of the
olefin, and release of the product through a -hydride elimination. A base
then regenerates the Pd(0) catalyst via reductive elimination and closes the
catalytic cycle. Two alternate mechanisms (one cationic) are shown below
with the same general sequence of steps.
+ [HBase]X PR3 + [HBase]X
R 3P Pd
R + PR3
R' R R' R
oxidative R 3P Pd PR3
addition
+X + R-X X
+ Base - PR3 + + Base
R'
H R R R H R
R3P Pd R 3P Pd X R3P Pd R3P Pd

PR3 R' PR3 X R' X R'

-hydride X + migratory -hydride

elimination insertion elimination
R'
H H
H H R
R R
R 3P Pd H
R3P Pd H R 3P Pd R'
migratory X
R' R'
PR3 insertion PR3

The Heck reaction differs significantly from the earlier Pd(0)-catalyzed

cross-coupling reactions because:
1) it involves an insertion after the oxidative addition step
2) the catalytic cycle is closed with a -hydride elimination, whereas
the other couplings end with a reductive elimination.
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 8

In the -hydride elimination step, the palladium and hydride must be

coplanar for the reaction to take place, as this is a syn elimination process.
For steric reasons, the R group will tend to eclipse the smallest group on the
adjacent carbon as elimination occurs, leading predominantly to a trans
double bond in the product.
PdLX
H R
X
+ H Pd
R H L
H R' R'
major product

PdLX
H
X
+ H Pd
H H R R' L
R R'
minor product

Applications of the Heck reaction in organic synthesis

Pd(OAc)2 5 mol-%
P(o-Tol)3 20 mol-% O
O OEt O
HO2C Br + HO2C
O Et3N, 100 
C OEt

O
Pd(OAc)2 5 mol-%
Br P(o-Tol)3 20 mol-%
OEt OEt
+
O Et3N, DMF
87% yield

Pd(dba)2 3 mol-%
OTf L* 6 mol-%
+ O
O i-Pr2NEt, THF O
L* = PPH2 N
87% yield, 98% ee
t-Bu
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 9

Sonogashira Coupling
The coupling of terminal alkynes with aryl or vinyl halides under palladium
catalysis is known as the Sonogashira reaction. This catalytic process
requires the use of a palladium(0) complex, is performed in the presence of
base, and generally uses copper iodide as a co-catalyst.
alkyne
Pd(0)
R-X + R' R R' + HX
aryl or
vinyl halide
The mild conditions usually employed (frequently room temperature) mean
that the Sonogashira coupling can be applied to thermally sensitive
substrates. The mechanism of the reaction is similar to that of the Stille and
Suzuki couplings. Oxidative addition of the organic halide gives a Pd(II)
intermediate that undergoes transmetallation with the alkynyl copper
(generated from the terminal alkyne, base, and copper iodide). Reductive
elimination with coupling of the two organic ligands gives the product and
regenerates the Pd(0) catalyst.
PdL2 R X
R R'

R R
L2Pd L2Pd
X

R' CuX Cu R'

Et3NH + C R' Et3NH X

Et3N + H R'
 Sabhuku Mudavanhu
Prof. Lionel Delaude, University of Liege in Belgium Cross-Coupling 10

As in the Heck reaction, It is often more convenient to use a stable and

soluble Pd(II) source such as Pd(PPh3)2Cl2 instead of Pd(0). This precursor is
rapidly reduced in situ to give a coordinatively unsaturated, catalytically
active, Pd(0) species. The geometry of the alkene is generally preserved so
that cis (Z) and trans (E) dichloroethylene give the two different geometrical
isomers of the enyne below in >99% stereochemical purity as well as
excellent yield.
Pd(PPh3)4, CuI
Cl Cl + H
BuNH2, rt, 5h
Cl 95% yield

Cl
Pd(PPh3)4, CuI
Cl + H
BuNH2, rt, 5h Cl
80% yield
 Sabhuku Mudavanhu

Polymerization & Metathesis

Polymerization is the reaction of an unsaturated organic reactant,

typically a C=C, with itself over and over again to produce a polymer
chain:
*
n * n
When only a few alkenes couple together to make a short chain, we refer
to that as oligomerization (oligomers are very short polymers).
There are typically three parts to most polymerizations:
Initiation: generating the active catalyst from a less active catalyst
precursor

LnM-Cl + AlR3 LnM-R + AlR2Cl

+ MAO (methylalumoxane)
+ ZnR2
LnM-Cl + H- LnM-H + Cl-

Propagation: the polymer chain growth portion of the reaction that

occurs over and over again
H3C H3C


M CH3 M CH3 M M

CH3
M
 Sabhuku Mudavanhu
Polymerization 2
Termination: a reaction step that stops the polymer chain growth

CH3
M H + CH3
M

H2
M H + CH3

In a good polymerization catalyst the initiation step generates as much

active catalyst as possible and the propagation step occurs as often as
possible, while the termination step is unlikely to happen. For early
transition metal catalysts the -hydride elimination step that can cause
termination is not that favorable.
A Living Catalyst is typically a polymerization catalyst in which all the
transition metal complexes present are the same and already in an active
catalytic state (no initiation step). When the substrate is added all the
catalyst molecules start the polymer chain growing steps at the same
time and same rate. This means that at any point the polymer chains
growing off each and every catalyst are all essentially the same length.
This leads to polymers that have a Mw/Mn value very close to 1.0.
What is Mw/Mn ? The average molecular weight of a polymer can be defined by Mn
and Mw. Mn is the simple average of total mass of the chains divided by the number
of chains. The weight average molecular weight Mw is the summation of the square
of the molecular weights divided by the summation of the molecular weights of all the
molecules present. In Mw more “weight” is provided to the to the higher molecular
weight polymers, while Mn treats all of them the same. The basis for Mw is that the
larger molecules contribute more to the properties of the polymer so they should
have more importance. Mw is always greater than Mn and the narrower the
distribution, the closer Mn and Mw are. The ratio of Mw to Mn is a measure of the
distribution of different length polymer chains. This ratio is referred to as the
dispersivity. As the distribution narrows, the dispersivity approaches a minimum
value of 1.0. Such a polymer referred to as mono disperse. Alternately as Mw/Mn
for a polymer increases (10 or 20) it is a referred to as poly-disperse. A standard
(narrow) Schultz-Flory statistical Mw/Mn polymer distribution is equal to 2.0.
 Sabhuku Mudavanhu
Polymerization 3
Some History: Ziegler-Natta Polymerization Catalysis

The German chemist Karl Ziegler (1898-1973) discovered in 1953 that when
TiCl3(s) and AlEt3 are combined together they produced an extremely active
heterogeneous catalyst for the polymerization of ethylene at atmospheric
pressure. Giulio Natta (1903-1979), an Italian chemist, extended the method to
other olefins like propylene and developed variations of the Ziegler catalyst based
on his findings on the mechanism of the polymerization reaction. The Ziegler-
Natta catalyst family includes halides of titanium, chromium, vanadium, and
zirconium, typically activated by alkyl aluminum compounds. Ziegler and Natta
received the Nobel Prize in Chemistry for their work in 1963.

The following is a short excerpt taken from Luigi Cerruti (International Journal
for Philosophy of Chemistry, 1999, vol 5, 3-41) on the initial work on the
oligiomerization and polymerization of ethylene:
In June 1953, they [Ziegler’s research group] investigated chromium, whose compounds gave
some butene but also a small amount of material with high molecular weight. This result was
encouraging. At the end of October, Breil, another of Ziegler’s collaborators, came to zirconium: a
rapid and complete polymerization occurred. Moreover, the infrared spectra demonstrated that the
polymer was linear. When the turn of titanium came up, the result was again striking. The reaction
was so fast that the vessel became hot, and the product was partially decomposed. Thus, the
problem was passed to Heinz Martin, who was looking for the mildest possible conditions of
polymerization. Since it was apparent that the system Ti/Al-alkyl was very active, Martin tried the
simplest possible conditions: no higher pressure at all and no external heating (Ziegler et al.
1955b, 543-544). The result of the trial was that Martin burst in Ziegler’s office waving a glass flask
and crying: "Es geht in Glass!"

The third generation of Ziegler-Natta catalysts were developed in 1960 with

Shell’s patent for a heterogeneous catalyst for propylene polymerization based on
TiCl4 supported on MgCl2. Montecatini and Mitsui independently patented
catalysts prepared from TiCl4, MgCl2 and an electron donator, and activated by a
mixture of trialkyl-Al with another electron donor in 1968. Industrial plants based
on these catalysts came online in the 1980’s. These third generation catalysts
brought a 50-fold increase in activity, so much so that the removal of the catalyst
from the final product was no longer necessary.
 Sabhuku Mudavanhu
Polymerization 4
Cossee (migatory insertion) vs. Green-Rooney (alkyidene
metallacycle) Propagation Mechanisms

The commonly accepted mechanism for polymer chain growth on a

transition metal catalyst is the very simple migratory insertion
mechanism initially proposed by Piet Cossee (Royal Shell labs) in 1964.
H3C H3C


M CH3 M CH3 M M

CH3
M

However in 1978 Malcolm Green and John Rooney proposed a rather

different mechanism based on the recently reported Schrock alkylidenes:

-hydride elimination
or
C-H oxidative addition

CH3 M M
M CH3 CH3
H H

CH3
CH3
M
CH3
M H M H

At the time this mechanism was very “sexy” since alkylidenes were
relatively new and quite the “rage”. A number of organometallic
researchers performed some rather elegant mechanistic studies to figure
out which mechanism was operating in a variety of polymerization
catalysts.
 Sabhuku Mudavanhu
Polymerization 5

One of the simplest studies involved the use of deuterated ethylene

mixed with regular ethylene:
Cp2TiCl(C2H5)
CD2=CD2 + CH2=CH2 C2H5-(CD2CD2)n(CH2CH2)n-H
Et2AlCl
HCl quench

If the migratory insertion mechanism was working, one should NOT get any scrambling of
the deuteriums and hydrogens in the polyethylene chain (easily confirmed by 1H and 2H
NMR). However, if the polymerization was working by the Green-Rooney metallacycle
mechanism, the -hydride elimination and subsequent H-alkyl reductive elimination steps
would lead to some scrambling of the H and D atoms. But no H/D scrambling was observed,
leading to conclusion that the polymerization was NOT working via the alkylidene-
metallacycle mechanism, supporting the simpler migratory insertion pathway.

Patricia Watson at Dupont performed another elegant study in 1984

using deuterium labeling:
Migratory insertion mechanism - no H/D scrambling
CH3

Cp2Lu CD3 + CH3

Cp2Lu
Cp2Lu CD3 CD3

H 3C
No H-D scrambling and high
regioselectivity supports the
migratory insertion mechanism for
this catalyst!

CH3
CH3

Cp2Lu CD 2 + CH3
Cp2Lu CD2 Cp2Lu CD2

D D D

Cp2Lu CD2
CH2D

H 3C

Alkylidene/metallacycle/reductive elimination
mechanism can lead to H/D scrambling
 Sabhuku Mudavanhu
Polymerization 6
The bottom line is that most mechanistic studies have clearly pointed to
the migratory insertion mechanism, certainly for the highly active
Group IV metals (Ti & Zr), for the lanthanides and actinides, and the
new late transition metal systems discovered by Brookhart and Gibson.
One proven exception is Schrock’s Ta alkylidene living catalyst that is
believed to work via the metallacycle mechanism:
observed in NMR

t-Bu t-Bu t-Bu t-Bu

Me3P PMe3 H H H
Ta (Me3P)3Ta (Me3P)3Ta (Me3P)3Ta
Me3P I I I
I I I I
I

(Me3P)3Ta t-Bu (Me3P)3Ta t-Bu

I I
I I

An interesting aspect of the migratory insertion reaction is that the most

active polymerization catalysts typically need to have an extra empty
orbital after the coordination of the alkene to the M-alkyl unit. Bercaw
has proposed that this is
because the alkyl group needs
to form an agostic C-H bond
interaction with the empty
orbital on the metal to tilt the
localized sp3 alkyl orbital away
from the metal and more
towards the alkene ligand to
promote the migratory
insertion. A transition-state
structure from a quantum
mechanical calculation showing this interaction is shown above.
 Sabhuku Mudavanhu
Polymerization 7
Polypropylene & Stereochemistry
The polymerization of propylene is slower and more complicated than
ethylene due to increasing steric factors and the generation of
stereochemistry on the polymer chain:

isotactic
* *
n

syndiotactic
* *
n

atactic (random)
* *
n

The steric environment around the metal center has a DRAMATIC

impact on what kind of stereochemistry one obtains.
C2 symmetry (chiral) - Isotactic polymer

Zr Zr
Polymer Polymer

Bulky-Small Catalyst environment - Syndotactic polymer

Zr SiMe2 Zr SiMe2

Polymer
N H2C Polymer N
t-butyl t-butyl
 Sabhuku Mudavanhu
Polymerization 8
A catalyst with small ligands that offer little steric directing effect, like
Cp2TiCl2, will generate atactic polypropylene.
In 1985 Walter Kaminsky discovered that the combination of
methylalumoxane and the Zr catalyst shown below generated a highly
active catalyst for isotactic polypropylene.

+ * Al O *
Zr methylalumoxane
Cl Cl (MAO)
CH3

Almost as active as Ziegler-Natta hetero catalyst

> 95% isotactic polypropylene

High MW and narrow polymer MW distribution

(semi-living catalyst)

meso isomer gives atactic polypropylene

Some History: Kaminsky, Bercaw & Metallocene Polymerization

The fourth generation of polymerization catalysts, based on metallocene
compounds, is now evolving towards industrial success. Their origin is very
interesting, because it was “accidental.” Kaminsky has described the incident
with these words:
“An accident in our laboratory in 1976 brought about equimolecular amounts of water
into the system compared to the trimethylaluminum, and, surprisingly, an unusual
high polymerization activity of ethylene was observed.”

Kaminsky and Sinn suspected that the water and AlEt3 reacted to form methyl
aluminoxane (MAO), and they subsequently discovered that MAO-activated
homogeneous metallocene catalysts were capable of polymerizing propene and
higher olefins. This seminal discovery by Kaminsky and Sinn started the search
for single-site catalysts.
 Sabhuku Mudavanhu
Polymerization 9
Late Transition Metal Polymerization Catalysts
Well characterized Group 8 polymerization catalysts were reported by Brookhart
in 1998 (J. Am. Chem. Soc. 1998, 120, 4050) and Gibson in 1999 (J. Am. Chem.
Soc. 1999, 121, 8728.). These catalysts operate via the simple Cossee alkene
addition and migratory insertion mechanism.
A key in preparing an efficient polymerization catalyst was the realization that
the facile -hydride eliminations occurring on Group 8 metals (especially Ni and
Pd) lead to an associative displacement problem that short circuited the chain
growth pathway. When a growing polymer alkyl chain does a -hydride
elimination from a 3-coordinated catalyst species, a 4-coordinate hydride-alkene
is formed.
R
-hydride R
R elimination R R'
N R' N
Ni Ni
N N H
R R
R R

associative ligand
displacement association

ligand R
R
dissocation R'
R R
N N
N
Ni + R' Ni
R H R N H
R R

A small ethylene can easily coordinate to the axial metal site leading to a less
stable 5-coordinate complex. This promotes loss of the longer alkene chain
leading to termination of the chain growth. By placing extremely bulky R-groups
on the diimine ligand, Brookhart was able to effectively block both axial
coordination sites while still allowing equatorial alkene coordination.
An unusual aspect of Brookhart’s Ni and Pd polymerization catalysts was that
they could produce highly branched polyethylene, with the amount of branching
controlled in large part by the ethylene pressure. Mechanistic studies indicated
that facile -hydride eliminations on these catalysts under lower ethylene
pressures enabled a “chain-walking” isomerization process shown below. This
leads to branching (sometimes extensive) of the growing polymer chain. Under
higher ethylene pressures, the empty coordination site needed for -hydride
elimination is more rapidly filled by an ethylene leading to more linear chain
growth.
 Sabhuku Mudavanhu
Polymerization 10

rotation of
R R alkene ligand R
R R R' R
N R' N N R'
Ni Ni Ni
R N N H R N H
R
R R R

R'
R'
R
ligand
R R
R R rotation R
N N N R'
Ni Ni Ni
R N H R N N
R
R R R

ligand
R addition R R
R R R
N N R' N
Ni R' Ni Ni
R N R N R N R'
R R R

polymer chain
growth continues

Metathesis
Metathesis catalysis refers to the reaction of two unsaturated substrates
(typically alkenes or alkynes) that leads to a switching of the atom
groups on each end of the bond with the unsaturation. This is shown
below for the reaction of two C8 dienes.

+
C8 C8

+
C14 C2
 Sabhuku Mudavanhu
Polymerization 11
The proposed mechanism for this involves metal-alkylidenes and is
shown below:
migratory ethylene
insertion elimination dissociation
M M M M

diene
addition

migratory
elimination
M M insertion M

Carrying this reaction out over and over with the more reactive terminal
double bonds leads to acyclic diene metathesis (ADMET)
polymerization with longer chain ,-diene substrates. The general
reaction relies on the loss of ethylene from the reaction mixture to drive
the reaction to high couplings and molecular weights. The internal
double bonds generated are not as reactive as the terminal double bonds
for the metathesis reaction.
Ring opening metathesis polymerization, ROMP, (Schrock, R. R.,
Acc. Chem. Res. 1990, 24, 158. Grubbs, R. H.; Tumas, W., Science,
1989, 243, 907) is another mechanism for polymerization related to the
Green-Rooney alkylidene pathway that can operate when one deals with
cyclic alkenes. The first commercial product using ROMP was prepared
by CdF Chimie from norbornene using a heterogeneous catalyst based
on MoO3 supported on alumnia.
 Sabhuku Mudavanhu
Polymerization 12

*
*

n
ROMP works best on cyclic alkenes that have some ring strain to
drive the ring opening process and minimize possible ring closing
reactions. A proposed mechanism for the ROMP of norbornene using a
Cp2Ti center is shown below. In this mechanism one considers the
alkylidene as a dianionic ligand, so the reaction with the alkene is
considered a migratory insertion. The subsequent elimination reaction
can proceed in two ways, backwards (non-productive) and forward,
which opens the norbornene ring and extends the polymer chain.

Cp2Ti Cp2Ti Cp2Ti

migratory
insertion

elimination

Cp2Ti

Cp2Ti Cp2Ti

migratory
insertion

Cp2Ti
elimination

Cp2Ti
 Sabhuku Mudavanhu

Homeworks
for the last 2 years

Followed by Answer Keys

 Sabhuku Mudavanhu
Organometallic Chemistry - 4571 Name: ______________________
Homework # 1: Due: February 8, 2007 (noon) Signature: __________________
Group: _____________________
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (38 pts) Sketch out a structure showing the geometry about the metal center as accurately as possible and
clearly show the electron counting for the complexes below. Phosphine ligand abbreviations are defined in
your notes (phosphine ligand section). Most molecules (some simplified) are from Organometallics, 2003, # 1
& 2, from the Library or on-line at the Library E-Journal site (only accessable from a campus computer).

a) Fe(η4-C4H4)(CO)3 (cover molecule) b) cis-[CpZrCl2(NMe2)2]−

c) Pd(NCN)Br (NCN ligand shown below) d) [Pd2(μ-CH3)(μ-CH2)(N-N)2]+ (one N-N

ligand shown below)

Me2N Me
N

Me2N N
Me

e) CpRuCl(Me2NCH2CH2NMe2) f) Cp2Y2(μ-H)2(NR2)2(THF)2

g) Ru(=CHMe)Cl2(PMe3)2 h) CpReCl2(η2-SCH2CH2S)
 Sabhuku Mudavanhu
HW # 1 – 2007 2
i) [CpFe(C6H6)]+ j) Cp2Nb(CH3)(CH2=CH2)

k) CpOs(H)(Cl)(SiMe3)(PR3) l) NiPh(PPh3)(N~O) N~O ligand shown below

R
N
O

m) cis-Re(CO)3(bipy)(NR2) bipy = bipyridine n) [Ru(C6H6)(C~N)(N≡CCH3]+ C~N below

NMe2

o) Cp2Fe2(μ-C≡C)(CO)4 p) [Cp2Fe]+

q) (C6H6)Cr(CO)3 r) Co2(μ-CO)2(CO)6
 Sabhuku Mudavanhu
HW # 1 – 2007 3

2. (12 pts) Propose an 18e- structure for the following metal/ligand combinations. Use at least one of each
metal and ligand listed. Complexes must be neutral. Don’t use more than 2 metal centers. Clearly show your
electron counting. Ligands are shown without charges, please indicate the proper ligand charge in your electron
counting. Draw a reasonable structure showing the geometry about the metal center(s).

a) Tc, Cp, O, P(OMe)3 b) Ni, dmpe (chelating), μ-CO, CO

c) Ta, Cp, C-R d) Cr, Cl, C≡NMe

 Sabhuku Mudavanhu
Organometallic Chemistry – 4571 Name: ______________________
Homework # 1: Due: February 14, 2008 (2 PM) Signature: __________________
Group: _____________________
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (38 pts) Sketch out a structure showing the geometry about the metal center as accurately as possible and
clearly show the electron counting for the complexes below. Phosphine ligand abbreviations are defined in
your notes (phosphine ligand section). All the examples below are from the 2007-08 Cambridge
Crystallographic Database (available from Prof. Stanley or Tigerware).

a) [Ru2(-acetate)4(H2O)2]+ b) [ReBr4(NO)(N≡CCH3)]

c) W(≡N)(NR2)3 d) AuI(PiPr3)

e) (6-C6H6)Co(2-RNCR=CH-RC=NR) f) [RuCl(SiCl3)2(CO)(PR3)]

g) [Os2(-OH)2(-acetate)(H2C=CH2)4(PR3)2]+ h) (5-indenyl)Rh(=CR2)(SbR3)
 Sabhuku Mudavanhu
HW # 1 – 2008 2
i) OsHCl2(N=Cy)(PR3)2 j) MoO2Cl2(2-MeSCH2CH2SMe)

k) Ti(NR)(CH2Ph)2(3-1,3,5-triazacyclohexane) l) [Ru2(-Cl)3(6-C6H6)2]+

m) Cp*2Cr2(-CH3)2(C6F5)2 n) Rh(acac)(CO)2

o) Ni(Ph)(CN)(dppe) p) Mo(CH3)5(OMe)

q) CpFe(CN)(CO)2 r) TpTi(2-Tp)(S-S) (Tp = trispyrazoleborate)

 Sabhuku Mudavanhu
HW # 1 – 2008 3

2. (12 pts) Propose an 18e- structure for the following metal/ligand combinations. Use at least one of each
metal and ligand listed. Complexes must be neutral. Don’t use more than 2 metal centers. Clearly show your
electron counting. Ligands are shown without charges, please indicate the proper ligand charge in your electron
counting. Draw a reasonable structure showing the geometry about the metal center(s).

a) Os, norbornadiene, Cl, pyridine b) Rh, Cp, Cl

c) W, Cl, NR, RC≡CR d) Y, Cp, Cl, THF

 Sabhuku Mudavanhu

Organometallic Chemistry - 4571 Name: ______________________

HW # 2 Due: March 15 (by Noon!), 2007 Signature: __________________
Group: _____________________
Check the box to the right if you want your graded homework to be placed out in the public rack outside Prof.
Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (20 pts) For each of the following pairs of metal complexes, circle the one that will have the highest CO
stretching frequency. Briefly discuss your reasoning for each case.

a) CpRe(CO)3 -or- Cp*Mn(PEt3)(CO)2

b) W(CH)Cl2(CH3)(PMe3)(CO) -or- Ta(NR)(CH3)(CO)2[P(OMe)3]2

c) PtCl4(CO)2 -or- [PtBr3(CO)]−

d) [Co(CO)4]− -or- [V(CO)6]−

e) CoF3(CO)3 -or- Cp*Mo(NO)(CO)2

2. (20 pts) For each of the following pairs of metal hydride complexes, circle the one that should have the
lowest pKa value. Briefly discuss your reasoning for each case.
a) Cp2Zr(H)(Br) -or- [CpMo(H)(CO)3]+
 Sabhuku Mudavanhu
HW#2 (2005) 2

b) H2Ru(C≡NCH3)2(CO)2 -or- H2Ru(PMe3)2(CO)2

c) Cp2V[P(OCF3)3](H) -or- [Cp2W(H)]−

d) HRh(CO)(PCy3)2 -or- HCo(CO)(PMe3)2

e) [HOs(PMe3)(dmpe)2]+ -or- HRe(CF3)2(CO)2[P(OMe3)3]2

4. (10 pts) Consider Cp2Rh2[μ-(CF3CCCF3)](CO)(CNR) shown on page 7 of the Alkene/Alkyne chapter.

The Rh-Rh bond distance is 2.67 Å strongly indicating the presence of a covalent bond between the two
rhodium atoms. (a) (5 pts) show the electron-counting for this complex including Rh oxidation state,
ligand charges, # of e- donated, etc. Only one Rh center needs to be counted since both the CO and
C≡NR ligands are neutral 2e- donors making the complex electronically symmetrical from an electron
counting viewpoint. (b) (5 pts) Why does the alkyne ligand orient parallel to the Rh-Rh bond? From an
organic hybridization and bonding viewpoint how should the “alkyne” be considered? Draw a simple
orbital picture showing how the filled “alkyne” orbitals are overlapping with the empty Rh orbitals (use
the diagram below as a starting point, ignore all other ligands).
 Sabhuku Mudavanhu

Organometallic Chemistry - 4571 Name: ______________________

HW # 2 Due: March 13, 2008 (by Noon) Signature: __________________
Group: _____________________
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (18 pts) For each of the following pairs of metal complexes, circle the one that should have the highest
average carbonyl IR stretching frequency. What does this tell you about the relative electron density on
the metal center (electron-rich or deficient)? Briefly discuss your reasoning for each case.

a) [Rh(CO)4] -or- [Fe(CO)4]2

b) [Re(PMe3)(N≡CMe)(CO)4]+ -or- [Mn{P(OPh)3}2(CO)4]

c) CpFe(Br)(CO)2 -or- Os(C-Me)(O)(CH3)3(CO)

d) Cp*Mn(PPh3)(CO)2 -or- CpIr(CO)2 (Cp* = C5Me5)

e) [Re(dmpe)2(PMe3)(CO)]+ -or- Ni(CO)3{P(OMe)3}

f) AuI(CO) -or- V(O)(CH3)(dppe)(CO)2

 Sabhuku Mudavanhu
HW#2 2008 2

2. (18 pts) For each of the following pairs of metal hydride complexes, circle the one that should have the
lowest pKa value. Briefly discuss your reasoning for each case.

a) HRe(CO)3(PPh3)2 -or- HRe(CO)3(dmpe)

b) Cp2Ti(Br)(H) -or- HCo(CO)4

c) [HRu(N≡CMe)(CO)4]+ -or- HCo(CO)(PEt3)3

d) TpOs(H)(CO)(NCCH3) -or- CpRu(H)(NCCH3)2 (Tp = tris(pyrazole)borate, see Lewis Base notes)

e) HRh(CO)(PCy3)2 -or- HIr(CO)(COD) (COD = cyclooctadiene)

f) HFe(NO)(CO)3 -or- Cp*2ZrH2

 Sabhuku Mudavanhu
HW#2 2008 3

3. (8 points) The nitrosyl ligand usually coordinates as a cationic ligand, NO+. It can, however,
occasionally act as an anionic NO ligand. When it is behaving as an anionic ligand it adopts a bent
coordination geometry. Discuss (using Lewis dot-like figures) the distribution of electrons in both kinds
of M-NO complexes and how these affect the structures (linear vs. bent). Assume in both cases that you
are dealing with a [M-NO]+ unit (positive charge on the overall complex) where the metal has 2 or more
d electrons. Clearly show the relative oxidation states of the metal and the relative d electron count for
each bonding case (linear vs. bent). I mentioned briefly in class that in some ways NO is the extreme
case of NO+ acting as a hyper -backbonding ligand. Explain what I meant by that statement.

4. (6 points) Circle the correct ordering of the following group of Fisher carbenes from the strongest
M=CR2 bond to weakest. Explain your reasoning.

Me2N NMe2 Me H Ph H MeO NMe2

a) b) c) d)
OC CO OC PMe3 OC CO OC CO
Cr Mo Cr W
OC CO OC PMe3 OC PMe2 Cl NO
C C
O PMe3 Me2P O

a>b>c>d b>c>d>a d>c>b>a c>a>d>b

 Sabhuku Mudavanhu
Organometallic Chemistry - 4571 Name: ______________________
HW # 3 Due: April 19 (by Noon), 2007 Signature: __________________
Group: _____________________
Check the box to the right if you want your graded homework to be placed out in the public rack outside Prof.
Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (30 pts) Identify the following reactions by their type (migratory insertion, elimination, β-hydride
elimination, oxidative addition, reductive elimination, ligand addition, ligand dissociation, ligand
coordination change, etc.). Note that in some cases you will have to use more than one description for a
reaction that has several steps. Note also that the order may be important! No discussion is needed.

a) CpIrCl(η3-allyl) + PMe3 CpIrCl(PMe3)(η1-allyl)

b) CpRh(CO)2 + CF3CF2Br CpRh(CO)(CF2CF3)Br + CO

c) H2Rh(PPh3)2(Cl)(CH2CH3) HRh(PPh3)2(Cl) + CH3CH3

O
d) CpFe(CO)2(Me) + PPh3 CpFe(CO)(acyl)(PPh3) (acyl = C )
CH3

e) PtCl2(CH2CH3)2(PMe3)2 PtCl2(PMe3)2 + CH2=CH2 + CH3CH3

f) [Cp2Mo(H)(CH2=CH2)]+ + PPh3 [Cp2Mo(CH2CH3)(PPh3)]+

 Sabhuku Mudavanhu
Organometallics Homework #3 (2007) 2

2. (20 pts) For each pair of complexes shown below, circle the one that should be the most reactive towards
the oxidative addition the substrate shown. Give a brief but clear explanation for your choice.

a) [Co(dmpe)2]+ -or- [Rh(dppe)2]+ Substrate = H2

b) RhCl(PPh3)3 -or- RhCl(CO)(PPh3)2 Substrate = CH3CH2Br

c) Co(CO)(PEt3)2Cl -or- Ir(CO)(PMe3)2Br Substrate = HSiMe3

d) Cr(CO)6 -or- W(CH)(CH3)3(dmpe) Substrate = CH3Cl

3. (10 pts) (η3-allyl)Co[P(OMe)3]3 is an arene hydrogenation catalyst that can cleanly hydrogenate benzene
to cyclohexane.
a) (5 pts) It is known that the first reaction step in the hydrogenation mechanism is H2 oxidative addition to
the complex. It is also known that there is no phosphine dissocation for this step. How does H2 add to
the complex? Discuss.
 Sabhuku Mudavanhu
Organometallics Homework #3 (2007) 3

b) (5 pts) The use of bulkier phosphite ligands such as P(OEt)3 or P(OiPr)3 speeds up the rate of arene
hydrogenation. Discuss the reason(s) for this observation. The statement in part a) does not necessarily
apply.

4. (20 pts) Consider the following reactions. Sketch out the final product clearly showing the structure and
geometry. The rxn steps listed may not be in the correct order. If they are NOT in the correct order
please include a brief and clear explanation of the correct order of steps and why they go in that order.

a) [Fe(CO)4]2− + CH3Br (oxidative addition)

b) [Ru(PMe3)(CO)4(acyl)]+ (elimination, ligand dissociation)

c) Ir(CH3)2Cl(dmpe) + N≡CCH3 (reductive elimination, ligand addition)

d) CpMo(H)(CH2=CHCH3)(dmpe) + 2CO (2 migratory insertions, 2 ligand additions)

 Sabhuku Mudavanhu
Organometallics Homework #3 (2007) 4

5. (20 pts) Shown below is a catalytic cycle for the cyclocoupling of CO2 and diynes developed by Prof.
Janis Louie at the University of Utah (JACS, 2002, 124, 15188).
a) (15 pts) Label the steps with boxes next to them. There may be more than one step shown in each
transformation. IPr ligand shown below.

O + CO2
O Ni(IPr)

IPr
Ni
O
C
Ni(IPr) O
O
O IPr
Ni
O

N N
..

IPr
b) (5 pts) The ligand is shown as a neutral ligand and Prof. Louie draws the bond from the IPr to the Ni as a
single bond. Is this correct? Clearly discuss.
 Sabhuku Mudavanhu

Orrganomettallic Che
emistry - 4571 Namee: ________________________
HW
W # 3 Due: April 10,
1 2008 (bby 2 PM) Signaature: ____________________
Group
p: _______________________
Check the boxx to the right if you
y want your graded homew work to be place
ed out in the puublic rack outsiide
Prof. Stanley’ss office. Otherwwise you will ha
ave to pick up your
y homeworkrk from Prof. Sttanley in personn:

1. (30
( pts) Preedict and skeetch out the structure
s for the transitioon-metal conntaining prodduct for the following
f
substitution reactions ussing one equuivalent of eaach the reacttants. State whether
w the mechanism is most
likely associative or disssociative annd reason(s) for your chooice.
a) CpFe(CH
H3)(CO)(H2C=CHCH
C 3) + PPh3

O)3(PMe3)2 + CH3−
b) ReCl(CO

mpe)(CO) + Br−
c) RuCl2(dm

d) W(CO)2(PEt3)4 + P(OMe)3

e) [Rh(CO))2(PPhMe2)2]+ + PEt3

f) CpTa(=C κ2-CF3NCF2CH2N(CH3)2) + CH2CHCH

CH2)(CH3)(κ C 2− (allyl)
 Sabhuku Mudavanhu
HW # 3 (2008) 2

2. (25 pts) Circle the ligand on the following complexes that will most easily dissociate. Briefly state the
reason(s) for your choice.

a) b) (R = alkyl groups)

c) d)

e) (R = Ph) f) (R = Me)

Pd O
R3P O S CF3
O

3. (10 pts) Re(O)(CO)4[P(OMe)3] reacts extremely quickly with one equivalent of PMe3 to do a CO ligand
substitution. Mn(OMe)(CO)3(dmpe), however, reacts far more slowly with PMe3 to do a CO ligand
substitution. Clearly state the reason(s) for this.
 Sabhuku Mudavanhu
HW # 3 (2008) 3

4. (15 pts) Consider the following allyl-mediated substitution reaction:

a) (8 pts) Label each forward-going reaction step in the boxes provided below the reaction (there may be
more than one fundamental reaction occurring in each setp, if so, label in the correct order).
b) (7 pts) Of the last two compounds, the final product is the most stable. Clearly state the reason(s) for
this.

5. (20 pts) To which of the following intact (no ligand dissociations) complexes can H2 do an oxidative
addition reaction to make a dihydride complex. Please circle Yes or No for each complex and clearly state
the reason(s) for this.
a) Cp2Ti(CO)2 Yes  -or- No b) Cr(CH)(CH3)2(dppe) Yes  -or- No

c) CpFeCl(PPh3) Yes  -or- No d) Pt(PPh3)3 Yes  -or- No

e) [Rh(CO)2(PMe3)3]+ Yes  -or- No

 Sabhuku Mudavanhu
Organometallic Chemistry - 4571 Name: ______________________
Homework # 4 - Due: May 1, 2007 (by Noon) Signature: __________________
Group: _____________________
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (20 pts) Write out a catalytic cycle for the hydrophenylation of alkenes to produce alkylated arenes:
R

R + +

The starting catalyst is shown below and you are to use benzene as the arene and ethylene (ethene) as the
alkene. The catalysis proceeds by the following reaction steps: 1) arene C-H oxidative addition, 2) alkene
addition, 3) migratory insertion, 4) reductive elimination. The exact ligands involved in step 3 is not specified,
you are to choose the most likely ligands to do this reaction. Ligand dissociation of the initial ligands is
allowed if necessary, but I have not indicated when this may (or may not) happen. Clearly sketch out each
metal complex with proper geometries. [Periana et al., JACS, 2000, 122, 7414-7415]

Ir(acac)(η4-benzene)

O
Ir
O
 Sabhuku Mudavanhu
HW # 4 – 2007 2

Read the attached paper from the Journal of the American Chemical Society (Bergman, 2001, 123, 2685-2686)
and answer the following questions about it.

2. (10 pts) The catalyst precursor used is listed as [RhCl(coe)2]2. What is coe? Sketch out the structure of
[RhCl(coe)2]2 – you can abbreviate the coe ligand as:

coe = ______________________

3. (15 pts) From Table 2 calculate the following:

a) maxium # of turnovers (TON): _______

b) average turnover frequency (TOF hr−1) for entry # 1 (assume 85% conversion to product) = ________

c) using the last catalytic run from Table 1, calculate the average TOF for this run = ________

4. (10 pts) In the scheme on the first page, column 2, substrate 1 can be isomerized to 2 or 3. Clearly, 1 can be
converted to the product 4. Can 2 or 3 directly cyclize to form 4? Explain your answer for 2 and 3.
 Sabhuku Mudavanhu
HW # 4 – 2007 3

5. (25 pts) Sketch out a catalytic cycle for 1 being converted to 4 (no isomerization). You only have to draw
the imidazole ring and N-alkenyl group on 1. Start with the catalyst shown below. The first step is
coordination of 1 via the less substituted N lone pair. The second step is activation (but label this with the
more correct mechanistic term) of the adjacent C-H bond. Based on this initial information, complete the
cycle. Clearly label each step with what is happening mechanistically.

Cy3P O
Rh
Cl O
 Sabhuku Mudavanhu
HW # 4 – 2007 4

6. (10 pts) At what point in the catalytic cycle is the alkene isomerization discussed in question # 4 (and the
paper) most likely to happen. Sketch out the isomerization of 1 to 2 and label each step (once again, you
don’t have to draw out the arene ring on 1 and 2).

7. (5 pts) Given the catalytic conditions (temp, catalyst loading, TOF), do you think the following similar
reaction is likely to be catalyzed by the best catalyst discussed in this paper? Fully discuss.
CH3 CH3

N N
+
N N

8. (5 pts) The authors add some excess PCy3, but I’ve only drawn the catalyst with one PCy3 ligand. Why
didn’t I use two PCy3 ligands on the catalyst?
 Sabhuku Mudavanhu
J. Am. Chem. Soc. 2001, 123, 2685-2686 2685

Annulation of Alkenyl-Substituted Heterocycles via with 10 mol % (Ph3P)3RhCl (Wilkinson’s catalyst) at 160 °C.
Rhodium-Catalyzed Intramolecular C-H Activated Monitoring the reaction by 1H NMR spectroscopy demonstrated
Coupling Reactions that 1 undergoes double bond positional isomerization rapidly
under the reaction conditions, leading to an initial mixture of
K. L. Tan, R. G. Bergman,* and J. A. Ellman* alkenes with the disubstituted isomer 2 predominating (eq 1). Over
time the mixture was converted to tricyclic product 4 and
Center for New Directions in Organic Synthesis decomposition products, contaminated only with trace amounts
Department of Chemistry, UniVersity of California† of 1, 2, and 3.
Berkeley, California 94720
ReceiVed December 12, 2000
Transition metal catalyzed C-H bond activation has been
developing rapidly as a method for the formation of carbon-
carbon bonds.1 One of the most useful transformations of this
type is directed C-H bond activation exemplified by the
regioselective ortho alkylation of aromatic carbonyl compounds
with ruthenium catalysts by Murai.2 Subsequently, several groups
have expanded the scope of intermolecular alkylation of arenes
by incorporating a variety of directing groups such as imines,
pyridines, and esters.3 Although broadly applicable, this inter-
molecular coupling occurs predominantly at the terminus of the
alkenyl chain, and thus gives only linear products. We report here
To optimize the reaction conditions, a range of phosphine
an intramolecular4 variant of this methodology that couples a vinyl
additives with varying steric and electronic properties were
carbon in a tethered alkene to imidazole rings via a novel and a
surveyed (Table 1). With [RhCl(coe)2]2 as the catalyst precursor,
selective C-H bond activation at the position R to the
the use of P(p-tolyl)3 resulted in 56% 1H NMR yield at 160 °C
heteroatom.5-8 This reaction is successful with a wide range of
after 40 h. Although the addition of P(t-Bu)3 did not improve the
substrates, allowing for the synthesis of a variety of annulated
yield, the addition of the electron-rich but less sterically encum-
heterocycles in good yield. In a significant departure from earlier
bering PCy3 effected the cyclization of alkene 1 to carbocycle 4
work, disubstituted and even trisubstituted alkenes have been
in 86% yield in 3.5 h at 160 °C as determined by 1H NMR
cyclized in a regioselective manner, yielding complex fused
spectroscopy. Isomerization to an intermediate mixture of alkenes
heterocyclic/carbocyclic skeletons with stereogenic centers.
1 and 2 was observed, with 2 predominating, and again both
In an effort to expand the scope of catalytic C-H activation
isomers were cleanly converted to product with further heating
and direct coupling to alkenes, we began by investigating the
(eq 1). Upon optimization of the conditions, it was found that 1
cyclization of N-homoallyl benzimidazole 1. Although attempts
cyclized to 4 in 79% isolated yield, with a reduction of catalyst
to cyclize 1 with RuH2CO(PPh3)3, Cp*Rh(C2H2SiMe3)2, [Rh-
loading to 5 mol % [RhCl(coe)2]2 and 7.5 mol % PCy3 (Table 2,
(Diphos)]22ClO4, and [RhCl(coe)2]2 proved unsuccessful, benz-
entry 1).
imidazole 1 was converted to carbocycle 4 in 60% 1H NMR yield
† The Center for New Directions in Organic Synthesis is supported by Table 1. Survey of Phosphine Effects on Cyclizationa
Bristol-Myers Squibb as Sponsoring Member. 1H
(1) For reviews, see: (a) Kakiuchi, F.; Murai, S. Activation of Unreactive phosphine time, h NMR yield, %
C-H Bonds. In Top. Organomet. Chem. 1999, 3, 47-79. (b) Guari, Y.; Sabo- PPh3 3.5 22 (61)b
Etienne, S.; Chaudret, B. Eur. J. Inorg. Chem. 1999, 1047-1055. (c) Dyker, P(o-tolyl)3 3.5 <5 (<5)b
G. Angew. Chem., Int. Ed. 1999, 38, 1699-1712. (d) Shilov, A. E.; Shul’pin, P(t-Bu)3 3.5 20 (57)b
G. B. Chem. ReV. 1997, 97, 2879-2932.
(2) (a) Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; P(p-tolyl)3 3.5 20 (56)b
Sonoda, M.; Chatani, N. Pure Appl. Chem. 1994, 66, 1527-1534. (b) Kakiuchi, PCy3 3.5 86
F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N.; Murai, S. a Reactions were preformed with 10 mol % [RhCl(coe) ] and 30
Bull. Chem. Soc. Jpn. 1995, 68, 62-83. 2 2
(3) (a) Lenges, C. P.; Brookhart, M. J. Am. Chem. Soc. 1999, 121, 6616- mol % PR3 at 160 °C in d8-toluene. b 1H NMR yield at complete
6623. (b) Lim, Y. G.; Kang, J. B.; Kim, Y. H. J. Chem. Soc., Perkin Trans. conversion.
1 1996, 2201-2206. (c) Lim, Y. G.; Kim, Y. H.; Kang, J. B. J. Chem. Soc.,
Chem. Commun. 1994, 2267-2268. (d) Jun, C. H.; Hong, J. B.; Kim, Y. H.; The reaction scope was quite general with respect to substitu-
Chung, K. Y. Angew. Chem., Int. Ed. 2000, 39, 3440-3441. (e) Trost showed
that alkenes could also be functionalized in similar fashion. Trost, B. M.; tion at the alkenyl group (Table 2). In an unprecedented direct
Imi, K.; Davies, I. W. J. Am. Chem. Soc. 1995, 117, 5371-5372. coupling of a C-H bond with a trisubstituted double bond,
(4) Murai has demonstrated directed intramolecular cyclization of 1,5 and tetracycle 12 was formed from 5 in good yield and high
1,6 dienes. Fujii, N.; Kakiuchi, F.; Yamada, A.; Chatani, N.; Murai, S. Bull.
Chem. Soc. Jpn. 1998, 71, 285-298. diastereoselectivity for the cis-ring fusion (15:1 by 1H NMR) as
(5) Jordan and Taylor showed the coupling of pyridine to propene. Jordan, established by X-ray crystallographic analysis (Table 2, entry 2).9
R. F.; Taylor, D. F. J. Am. Chem. Soc. 1989, 111, 778-779. Cyclization of 1,2-disubstituted alkene 6 yielded the five-
(6) Fujiwara has successfully cyclized electron-deficient alkenes and alkynes
to aromatic rings with palladium. Jia, C. G.; Piao, D. G.; Oyamada, J. Z.; Lu, membered ring 13 in good yield with no other cyclic products
W. J.; Kitamura, T.; Fujiwara, Y. Science 2000, 287, 1992-1995. observed (Table 2, entry 3). Six-membered rings were accessible
(7) Murai and Moore have shown the selective acylation of heteroaromatics with the appropriate substitution as demonstrated for products
with Ru3(CO)12. (a) Moore, E. J.; Pretzer, W. R.; O’Connell, T. J.; Harris, J.;
Labounty, L.; Chou, L.; Grimmer, S. S. J. Am. Chem. Soc. 1992, 114, 5888- 14 and 15 (Table 2, entries 4 and 5). Apparently, internal geminal
5890. (b) Chatani, N.; Fukuyama, T.; Kakiuchi, F.; Murai, S. J. Am. Chem. alkene substitution or allylic R,R-dibranching leads to the
Soc. 1996, 118, 493-494. (c) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J.
Org. Chem. 1997, 62, 2604-2610. (d) Fukuyama, T.; Chatani, N.; Tatsumi, (9) This result was unexpected, since insertion into the trisubstituted alkene
J.; Kakiuchi, F.; Murai, S. J. Am. Chem. Soc. 1998, 120, 11522-11523. is believed to initially form the trans-ring juncture. However, the rapid
(8) Intermolecular addition of C-H bonds in imines to alkenes has been isomerization seen in previous cases suggests that the cis- or trans-ring juncture
reported by Suggs et al. and Jun et al. (a) Suggs, J. W. J. Am. Chem. Soc. would be accessible, and our observations indicate that the cis adduct
1979, 101, 489-489. (b) Jun, C. H.; Lee, H.; Hong, J. B. J. Org. Chem. reductively eliminates more rapidly than the trans adduct (refer to Figure S-2
1997, 62, 1200-1201. in the Supporting Information for the mechanism).

10.1021/ja0058738 CCC: $20.00 © 2001 American Chemical Society

Published on Web 02/21/2001
 Sabhuku Mudavanhu
2686 J. Am. Chem. Soc., Vol. 123, No. 11, 2001 Communications to the Editor

Table 2. Rhodium-Catalyzed Cyclizationa

compound 7-d1 with 5 mol % catalyst and 7.5 mol % PCy3 at

135 °C afforded 14-d with deuterium incorporated at the two
positions indicated in eq 2. This result is consistent with rapid
alkene insertion and β-hydride elimination before the formation
of the final product.10 Analysis of 14-d by electrospray mass
spectrometry revealed that deuterium was exchanged between
molecules during the course of its formation, since in the mass
spectrum of the product, mass ions for 14-d0, -d1, -d2, and -d3
were observed. Notably, reaction of alkene 7 under catalytic
conditions in d8-toluene showed no deuterium incorporation into
7 or 14, ruling out exchange of deuterium with the solvent. The
proposed intermolecular deuterium exchange was confirmed by
the following crossover experiment (Figure 1). Carrying out the
catalytic reaction with a 50:50 mixture of 9 and 1-d1 gave products
16-d and 4-d, which were both shown to have deuterium
incorporated by 1H NMR and mass spectrometry. The crossover
could be occurring through an intermolecular alkene insertion
followed by rapid β-elimination, allowing for scrambling of
deuterium between molecules. In light of the rapid intermolecular
deuterium exchange observed here, it is interesting that no
intermolecular coupling was observed. Furthermore, attempts to
couple N-methylbenzimidazole to neo-hexene proved unsuccess-
ful.

a Reactions were run with 5% [RhCl(coe) ] and 7.5% PCy at 160

2 2 3
°C for 20 h in THF unless otherwise noted. b Reactions were run with
10% [RhCl(coe)2]2 and 15% PCy3 at 180 °C for 20 h in toluene.
c Reaction was run with 10% [RhCl(coe) ] and 15% PCy at 180 °C
2 2 3
for 3 days. d 75% yield of cis; diastereoselectivity of 15:1 based on 1H Figure 1. Deutrium crossover experiment.
NMR.
In summary, we have developed a general method for carbon-
exclusive formation of the larger rings. Geminal substitution may carbon bond formation without necessitating pre-functionalization
favor the six-membered ring due to the difficulty of cyclizing to of the reaction partners. The new carbocyclization can be used
form a quaternary center. to form both five- and six-membered rings via catalytic C-H
In addition to modulating the regioselectivity, the level of bond activation. A range of substrates including mono-, di-, and
substitution at the alkenyl position also has a dramatic impact on trisubstituted alkenes has allowed the formation of complex
the rate of the reaction. Both 1,2-disubstituted alkene 6 and structures with stereogenic centers. Mechanistic studies and
trisubstituted alkene 5 require more vigorous conditions than application to other heterocyclic classes are under way.
alkenes 1 and 9 to effect complete cyclization. Interestingly,
terminal alkene 10 cyclizes more slowly than geminally substi- Acknowledgment. This work was supported by the NIH GM50353
tuted alkene 9 and monosubstituted alkene 1, even though all three (to J.A.E), the Director and Office of Energy Research, Office of Basic
yield five-membered carbocycles (Table 1, entries 7, 6, and 1). Energy Sciences, Chemical Sciences Division, U.S. Department of Energy,
Monitoring the cyclization of 9 to 16 by 1H NMR spectroscopy under Contract No. DE-AC03-76SF00098 (to R.G.B). We thank Dr. Fred
Hollander and Dr. Alan Oliver of the UC Berkeley CHEXRAY facility
shows that 9 does not undergo much double bond isomerization
for carrying out the X-ray diffraction studies.
during the reaction, which may account for at least part of the
difference in reactivity of 9 versus 10. In addition, geminal Supporting Information Available: Experimental details, including
substitution may provide an enhancement in the overall rate. The analytical data for all compounds described in the article, a possible
successful cyclization of imidazole 11 raises the possibility of mechanism for formation of 12, and X-ray diffraction data for 12 (PDF).
extending the scope of this chemistry to other heterocycles. This material is available free of charge via the Internet at http://pubs.acs.org.
In an effort to obtain preliminary information about the
JA0058738
mechanism of these cyclizations, deuterium tracer (eq 2) and
crossover experiments (Figure 1) were undertaken. Treatment of (10) Similar results were observed by Murai in ref 4.
 Sabhuku Mudavanhu

Organometallic Chemistry - 4571 Name: ______________________

Homework # 4 Signature: __________________
Due: Tuesday, April 29, 2008 (by 2 PM) Group: _____________________
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (20 pts) Starting with the catalyst shown below (and the first step) sketch out the catalytic cycle for the
trimerization of ethylene to make 1-hexene. Clearly label each step.

Cl
Ph2
P
N Cr
P
Ph2 Cl 2

Ph2
Cl
P
N Cr
P
Ph2 Cl
 Sabhuku Mudavanhu
Organometallics HW # 4 (2008) 2

Read the attached paper from the Journal of the American Chemical Society (Shirakura & Suginome, 2008,
130, 5410-5411) and answer the following questions about it.

2. (10 pts) What is the likely nickel catalyst (what the authors refer to as Ni(0)Ln) that initially reacts with the
alkyne? Sketch out this species and indicate its overall electron-count and d-electron count. Use the
phosphine ligand that the authors report works best for this catalyst. Briefly discuss why did you chose this
compound?

3. (10 pts) From Table 1 calculate the following for entry # 11 (assume 100% conversion to product):

a) # of turnovers (TON): _______

b) average turnover frequency (TOF, hr−1) = ________

4. (10 pts) Why doesn’t’ P(OBu)3 work as a ligand for this catalytic reaction relative to PBu3?

5. (20 pts) Label the lettered steps in the authors proposed catalytic cycle (all steps proceeding clockwise). If
there is more than one step, list them in the correct order.

A=

A
B=
C

C=

B
 Sabhuku Mudavanhu
Organometallics HW # 4 (2008) 3

6. (30 pts) Sketch out a catalytic cycle for the dimerization of two of the alkyne reactants to give the side
product 4a (SiMe3 group). Clearly label each reaction step and show the catalyst complex involved in each
step. Start with the catalyst complex shown below (no phosphine ligands involved in this cycle).

SiMe3
SiMe 3

Ni H H

H
SiMe3
 Sabhuku Mudavanhu

Published on Web 04/02/2008

Nickel-Catalyzed Addition of C-H Bonds of Terminal Alkynes

to 1,3-Dienes and Styrenes
Masamichi Shirakura and Michinori Suginome*
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering,
Kyoto UniVersity Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
Received February 8, 2008; E-mail: [email protected]

Catalytic reactions involving addition of C-H bonds across Table 1. Ni-Catalyzed Hydroalkynylation of 1,3-Diene 1a with 2a
carbon-carbon multiple bonds have presented a great challenge
in synthetic organic chemistry during the past decade, aiming at
exploration of efficient and selective synthetic methods for organic
compounds.1,2 Among the various C-H bonds, sp-C-H bonds
have been the primary target for activation by virtue of the relatively
high acidity of the hydrogen atoms on the sp-hybridized carbon
entry Si ligand %yield of 3b %yield of 4b
atom. For instance, addition of hydrogen cyanide to carbon-carbon
multiple bonds has been studied extensively, offering convenient 1 Me3Si (2a) PCy3 16 nd
2 PhMe2Si (2b) PCy3 15 nd
methods for the synthesis of nitrile derivatives.3 Studied even more 3 Ph2MeSi (2c) PCy3 14 nd
extensively have been catalytic additions of alkyne C-H bonds. 4 t-BuMe2Si (2d) PCy3 32 nd
Transition-metal-catalyzed dimerization of alkynes through inser- 5 i-Pr3Si (2e) PCy3 57 11
6 i-Pr3Si (2e) none 0 83
tion of the carbon-carbon triple bond into the alkyne C-H bond 7 i-Pr3Si (2e) P(OBu)3 0 0
has been achieved using a variety of transition metal catalysts,4 8 i-Pr3Si (2e) P(t-Bu)3 0 30
leading to success in cross-dimerization systems, in which two 9 i-Pr3Si (2e) PPh3 65 12
10 i-Pr3Si (2e) PMe3 95 trace
different alkynes are selectively coupled.5 The alkyne dimerization 11 i-Pr3Si (2e) PBu3 99 (84) 0
may proceed through oxidative addition of the sp-C-H bond to
transition metal catalysts to generate (hydro)(alkynyl)metal inter- a
All reactions were performed on a 0.1 mmol scale in toluene (0.5
mediates, which undergo further insertion of alkyne. Although it M) for 4 h using 10 mol % of Ni(cod)2 with 40 mol % of phosphine
seems easy to extend these reaction intermediates to hydroalky- ligands. b 1H NMR yields. Isolated yield is in the parentheses.
nylation of other unsaturated organic molecules such as alkenes,
there have been only a few examples for the hydroalkynylation of system, homodimerization of 2e took place exclusively. A PPh3-Ni
unsaturated molecules other than alkynes. Those reported hy- catalyst exhibited catalytic activity comparable to that of the
droalkynylation reactions require cyclopropenes,6 allenes,7 and PCy3-Ni catalyst (entry 9). It was eventually found that sterically
norbornadiene8 as the reaction partners, in which the CdC bonds less demanding trialkylphosphines such as PMe3 and PBu3 invested
are highly reactive because of the ring strain or the cumulative the catalyst system with remarkable activity toward the hydroalky-
CdC bonds. Addition to 1,3-dienes has only been partly achieved nylation (entries 10 and 11).
in the ruthenium-catalyzed codimerization.9 Expansion of the In the presence of the PBu3/Ni(cod)2 catalyst, several 1,3-dienes
reaction scope has long been pursued in recognition of the reacted with 2e at room temperature (Table 2). In addition to 1a,
importance of the development of new synthetic routes to alkyne 1-aryl-1,3-butadienes bearing electron-donating (1b) as well as
derivatives, but with no particular success. Herein, we describe electron-withdrawing groups (1c) on the aromatic ring selectively
the nickel-catalyzed addition of the alkyne C-H bond across a produced the corresponding 1,4-enynes in high yields (entries 1–3).
carbon-carbon double bond of 1,3-dienes, styrenes, and norbornene. Note that the reaction proceeded even at room temperature with 1
In the course of our research project aiming at nickel-catalyzed mol % of catalyst loading. The geometry of the CdC bond of the
alkynylation of carbon-carbon triple bonds,10 we carried out product was found to be >99% trans, in spite of the fact that the
reactions of silylacetylenes 2a-e with 1-phenyl-1,3-butadiene 1a starting dienes were used as mixtures of trans and cis isomers with
in the presence of nickel catalysts (Table 1). It is interesting to varied E:Z ratios. 1,3-Pentadiene (1d), an aliphatic terminal
note that reactions of trimethylsilyl- (2a), dimethylphenylsilyl- (2b), conjugated diene, afforded the corresponding 2-alkynylation prod-
and methyldiphenylsilylacetylene (2c) produced the corresponding uct 3de in high yield (entry 4). A conjugated triene 1e cleanly
hydroalkynylation products, albeit in low yields (entries 1–3). The underwent the addition of 2e, giving dienyne 3ee in good yield
yield was improved by using more bulky silylacetylenes such as (entry 5). A conjugated silyl enol ether 1f also gave the corre-
tert-butyldimethylsilyl- (2d) (32%) and triisopropylsilylacetylene sponding silyl enol ether 3fe, in which the siloxy-substituted CdC
(2e) (57%) (entries 4 and 5). The effect of the bulky silyl groups bond was left untouched (entry 6). In this particular reaction, a
can be ascribed to retardation of homodimerization and oligomer- decrease in the catalyst loading to 5 mol % in Ni resulted in the
ization of the alkynes, as pointed out in previous reports on the reaction remaining incomplete. Reaction of cyclic diene 1g with
alkyne cross-dimerization.5f The phosphorus ligand was then varied 2e proceeded efficiently at room temperature, giving 3-ethynyl-
(entries 6–11). A ligand-free catalyst (entry 6), phosphite-based cyclohexene derivative 3ge in high yield (entry 7). Note that
(entry 7), or PtBu3-based nickel catalysts (entry 8) resulted in no isoprene, 2,3-dimethyl-1,3-butadiene, and 1,1-diphenyl-1,3-buta-
formation of the hydroalkynylation product. In the ligand-free diene were found to be unreactive under the current reaction
5410 9 J. AM. CHEM. SOC. 2008, 130, 5410–5411 10.1021/ja800997j CCC: $40.75  2008 American Chemical Society
 Sabhuku Mudavanhu
COMMUNICATIONS
Table 2. Scope of the Nickel-Catalyzed Hydroalkynylation of ing π-allylnickel species have been proposed in the nickel-catalyzed
1,3-Dienesa hydrovinylation11 and hydrocyanation12 of 1,3-dienes.
The catalyst system could be applicable to hydroalkynylation
of other unsaturated organic compounds. Norbornene underwent
1,2-alkynylation, producing exo-addition product 5 stereoselectively
(eq 1). The most striking application may be the hydroalkynylation
of styrene derivatives 6a and 6b, in which the alkynyl groups were
introduced to the internal carbon atoms of the CdC bonds to give
products 7a and 7b (eq 2).

In summary, addition of an alkynyl C-H bond to the CdC bond

of 1,3-dienes, styrenes, and norbornene has been developed using
nickel catalysts. Use of sterically less demanding trialkylphosphines
as a ligand in combination with bulky silylacetylenes such as 2e
as a substrate is crucial to attain a high yield.
Acknowledgment. This work was supported by a Grant-
in-Aid for Scientific Research on Priority Areas “Advanced
Molecular Transformations of Carbon Resources” from
MEXT.

Supporting Information Available: Experimental procedures

and spectral data for the new compounds. This material is available
free of charge via the Internet at http://pubs.acs.org.
a
Reactions were performed with 3.0 equiv of dienes on a 0.3 mmol References
scale in toluene (1.5 M) in the presence of Ni(cod)2 (1.0–10 mol %) with
PBu3 (P/Ni ratio ) 4/1), unless otherwise noted. b Isolated yields. c A (1) (a) Dyker, G., Ed. Handbook of C-H Transformations; Wiley-VCH:
Weinheim, Germany, 2005. (b) Kakiuchi, F. Murai, S. In ActiVation of
gram-scale reaction with 1.09 g (6.0 mmol) of 2e with 1.1 equiv of 1a. UnreactiVe Bonds and Organic Synthesis; Murai, S., Ed.; Springer: Berlin,
Heidelberg, 1999; p 48. (c) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. ReV.
Scheme 1. Possible Mechanism of the Ni-Catalyzed 2002, 102, 1731.
Hydroalkynylation Reaction (2) (a) Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda,
M.; Chatani, N. Nature 1993, 366, 529. (b) Godula, K.; Sames, D. Science
2006, 312, 67.
(3) (a) Jackson, W. R.; Lovel, C. G. J. Chem. Soc., Chem. Commun. 1982,
1231. (b) Ikeda, S. In Modern Organonickel Chemistry; Tamaru, Y., Ed.;
Wiley: Weinheim, Germany, 2005; p 102.
(4) (a) Bustelo, E.; Dixneuf, P. H. In Handbook of C-H Transformations;
Dyker, G., Ed.; Wiley-VCH: Weinheim, Germany, 2005, p 62. (b) Ogoshi,
S.; Ueta, M.; Oka, M.; Kurosawa, H. Chem. Commun. 2004, 2732.
(5) (a) Trost, B. M.; Chan, C.; Ruhter, G. J. Am. Chem. Soc. 1987, 109, 3486.
(b) Trost, B. M.; McIntosh, M. C. Tetrahedron Lett. 1997, 38, 3207. (c)
Trost, B. M.; Sorum, M. T.; Chan, C.; Harms, A. E.; Rühter, G. J. Am.
Chem. Soc. 1997, 119, 698. (d) Yi, C. S.; Liu, N. Organometallics 1998,
17, 3158. (e) Katagiri, T.; Tsurugi, H.; Funayama, A.; Satoh, T.; Miura,
M. Chem. Lett. 2007, 36, 2007. (f) Tsukada, N.; Ninomiya, S.; Aoyama,
Y.; Inoue, Y. Org. Lett. 2007, 9, 2919. (g) Nishimura, T.; Guo, X.-X.;
Ohnishi, K.; Hayashi, T. AdV. Synth. Catal. 2007, 349, 2669.
(6) Yin, J.; Chisholm, J. D. Chem. Commun. 2006, 632.
(7) (a) Trost, B. M.; Kottirsch, G. J. Am. Chem. Soc. 1990, 112, 2816. (b)
Yamaguchi, M.; Omata, K.; Hirama, M. Tetrahedron Lett. 1994, 35, 5689.
(c) Bruyere, D.; Grigg, R.; Hinsley, J.; Hussain, R. K.; Korn, S.; De La
conditions. Gaseous butadiene (1h) (1 atm), on the other hand, Cierva, C. O.; Sridharan, V.; Wang, J. Tetrahedron Lett. 2003, 44, 8669.
(d) Rubin, M.; Markov, J.; Chuprakov, S.; Wink, D. J.; Gevorgyan, V. J.
produced the hydroalkynylation products in good yield (entry 8). Org. Chem. 2003, 68, 6251.
In contrast to the hydroalkynylation of other dienes, butadiene (8) Tenaglia, A.; Giordano, L.; Buono, G. Org. Lett. 2006, 8, 4315.
(9) Mitsudo, T.; Nakagawa, Y.; Watanabe, K.; Hori, Y.; Misawa, H.; Watanabe,
produced a 2:3 mixture of two enyne isomers. One isomer (3he) H.; Watanabe, Y. J. Org. Chem. 1985, 50, 565.
formed in a minor quantity has been obtained through the expected (10) (a) Yamamoto, A.; Suginome, M. J. Am. Chem. Soc. 2005, 127, 15706.
(b) Suginome, M.; Shirakura, M.; Yamamoto, A. J. Am. Chem. Soc. 2006,
1,2-addition reactions, whereas the major isomer was the 1,4- 128, 14438.
hydroalkynylation product 3he′. The formation of the 1,4-addition (11) (a) Zhang, A.; RajanBabu, T. V. J. Am. Chem. Soc. 2006, 128, 54. (b)
isomer, as well as the exclusive formation of the trans-products Rajanbabu, T. V. In ComprehensiVe Asymmetric Catalysis; Jacobsen, E.,
Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. 1, p 417.
from the E/Z mixtures of the starting 1,3-dienes, indicates that the (12) Bini, L.; Müller, C.; Wilting, J.; von Chrzanowski, L.; Spek, A. L.; Vogt,
catalytic hydroalkynylation proceeds through the formation of a D. J. Am. Chem. Soc. 2007, 129, 12622.
π-allylnickel intermediate (Scheme 1). Similar mechanisms involv- JA800997J

J. AM. CHEM. SOC. 9 VOL. 130, NO. 16, 2008 5411

 Sabhuku Mudavanhu
Organometallic Chemistry - 4571 ANSWER KEY
Homework # 1: Due: February 8, 2007
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (38 pts) Sketch out a structure showing the geometry about the metal center as accurately as possible and
clearly show the electron counting for the complexes below. Phosphine ligand abbreviations are defined in
your notes (phosphine ligand section). Most molecules (some simplified) are from Organometallics, 2003, # 1
& 2, from the Chem Library or on-line at the Library E-Journal site (only accessable from a campus computer).

a) Fe(η4-C4H4)(CO)3 (cover molecule) b) cis-[CpZrCl2(NMe2)2]−

Fe(0) d8 Zr(+4) d0
η4-C4H4 4e- Cp− 6e-
3 CO 6e- 2 NMe2− 8e-
Fe Me2 N Zr Cl 2 Cl− 4e-
OC Total 18e-
C Cl Total 18e-
C O Me 2N
C4H4 is cyclobutadiene, a
O neutral 4e- donor

c) Pd(NCN)Br (NCN ligand shown below) d) [Pd2(μ-CH3)(μ-CH2)(N-N)2]+ (one N-N

ligand shown below)

Me 2N Pd(+2) d8 Me Me Pd(+2) d8
NCN− 6e- N H2 N-N 4e-
N
Br− 2e- C μ-CH22− 2e-
Br Pd
Total 16e- Pd Pd μ-CH3− 1e-
C Pd-Pd 1e-
N H3 N
Me 2N Total 16e-
Me Me

e) CpRuCl(Me2NCH2CH2NMe2) f) Cp2Y2(μ-H)2(NR2)2(THF)2
Y(+3) d0
Ru(+2) d6 Cp− 6e-
Cp− 6e- 2 μ-H− 2e-
O NMe 2
2 NR3 4e- THF 2e-
Ru Cl− 2e- Y
H
Y NMe2− 4e-
NMe2 H
Cl Total 18e- O Total 14e-
Me 2N NMe 2 No Y-Y bonding due to d0
electron count!

g) Ru(=CHMe)Cl2(PMe3)2 h) CpReCl2(η2-SCH2CH2S)
Ru(+4) d4
PMe 3 =CHR2− 4e- Re(+5) d2
2 PR3 4e- Cp− 6e-
Cl 2 Cl− 4e- 2 SR− 4e-
Ru 2 Cl− 4e-
Total 16e-
Cl
Re
Cl S Total 16e-
Also OK to count the =CHR
PMe 3 group as a neutral carbene Cl S
that is a 2e- donor – you will
still get the same total e-
count
 Sabhuku Mudavanhu
HW # 1 – 2007 2
i) [CpFe(C6H6)]+ j) Cp2Nb(CH3)(CH2=CH2)

Fe(+2) d6 Nb(+3) d2
C6H6 6e- 2 Cp− 12e-
Cp− 6e- H2C=CH2 2e-
Fe Nb
CH 3 CH3− 2e-
Total 18e-
Total 18e-

k) CpOs(H)(Cl)(SiMe3)(PR3) l) NiPh(PPh3)(N~O) N~O ligand shown below

Os(+4) d4 Ph 3P Ni(+2) d8
Cp− 6e- N~O− 4e-
R
SiR3− 2e- N
Ni PPh3 2e-
H- 2e- Ph− 2e-
H
Os PR3 2e-
O
PR 3 Total 16e-
Cl− 2e-
Cl SiMe3 Total 18e-

m) cis-Re(CO)3(bipy)(NR2) bipy = bipyridine n) [Ru(C6H6)(C~N)(NCCH3]+ C~N below

Re(+1) d6 Ru(+2) d6
NR2− 2e- C~N− 4e-
bipy 4e- C6H6 6e-
N Ru
OC NR 2 3 CO 6e- N
C NCCH3 2e-
CH 3
Re Total 18e- NMe 2 Total 18e-
N
OC
C
O

o) Cp2Fe2(μ-C≡C)(CO)4 p) [Cp2Fe]+

O O
Fe(+2) d6 Fe(+3) d5
C C Cp− 6e- 2 Cp− 12e-
Fe Fe
μ-C≡C2− 2e- Total 17e-
2 CO 4e- Fe
OC
C Total 18e-
O

q) (C6H6)Cr(CO)3 r) Co2(μ-CO)2(CO)6

Cr(0) d6 OC O CO Co(0) d9
C
C6H6 6e- 2 μ-CO 2e-
3 CO 6e- Co Co 3 CO 6e-
OC C
CO
Cr C O C 1 Co-Co 1e-
OC Total 18e-
C O O
C O Total 18e-
O
 Sabhuku Mudavanhu
HW # 1 – 2007 3

2. (12 pts) Propose an 18e- structure for the following metal/ligand combinations. Use at least one of each
metal and ligand listed. Complexes must be neutral. Don’t use more than 2 metal centers. Clearly show your
electron counting. Ligands are shown without charges, please indicate the proper ligand charge in your electron
counting. Draw a reasonable structure showing the geometry about the metal center(s).

a) Tc, Cp, O, P(OMe)3 b) Ni, dmpe (chelating), μ-CO, CO

O
Tc(+3) d4 C O CO Ni(0) d10
Cp− 6e- C
2 μ-CO 2e-
O2− 4e- Ni Ni CO 2e-
R 2P PR 2
2 PR3 4e- C 2 PR3 (dmpe) 4e-
Tc PR 2 O R2P
P(OMe)3 Total 18e- Total 18e-
O
P(OMe)3

c) Ta, Cp, C-R d) Cr, Cl, C≡NMe

Ta(+5) d0 Cl Cl Cr(+2) d4
2 Cp− 12e- RN NR 2 Cl− 4e-
CR3− 6e- C C 5 C≡NR 10e-
Cr
Ta C R Total 18e- C C Total 18e-
RN C NR
7-coordinate Cr with
“skinny” ligands is A-OK
N
R
 Sabhuku Mudavanhu

Organometallic Chemistry – 4571 ANSWER KEY

Homework # 1: Due: February 14, 2008
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (38 pts) Sketch out a structure showing the geometry about the metal center as accurately as possible and
clearly show the electron counting for the complexes below. Phosphine ligand abbreviations are defined in
your notes (phosphine ligand section). All the examples below are from the 2007-08 Cambridge
Crystallographic Database (available from Prof. Stanley or Tigerware).

a) [Ru2(μ-acetate)4(H2O)2]+ b) [ReBr4(NO)(N≡CCH3)]−
Me
Ru(+2) d6 Ru(+3) d5 Re(+2) d5
O O Me H 3O 2e- H3O 2e- NCMe 2e-
4 μ-acetate− 8e- 4 μ-acetate− 8e- NO+ 2e-
4Br−
O O
Total: 16e- Total: 15e- 8e-
H2O Ru Ru OH2
Total: 17e-
O O This is a mixed oxidation state
system with an average Ru oxidation
O O state of +2.5 via resonance. The
dashed line between the Ru
Me represents this resonance.

c) W(≡N)(NR2)3 d) AuI(PiPr3)

W(+6) d0 Au(+1) d10

N3− 6e- PR3 2e-
3NR2− 12e- I− 2e-
Total: 18e- Total: 14e-

e) (η6-C6H6)Co(κ2-RNCR=CH-RC=NR) f) [RuCl(SiCl3)2(CO)(PR3)]−

Co(+1) d8 Ru(+2) d6
NR2− 2e- 2SiCl3− 4e-
NR3 2e- Cl− 2e-
C 6H 6 6e- PR3 2e-
Total: 18e- CO 2e-
Total: 16e-

g) [Os2(μ-OH)2(μ-acetate)(H2C=CH2)4(PR3)2]+ h) (η5-indenyl)Rh(=CR2)(SbR3)

Os(+2) d6 Rh(+3) d6
μ-acetate− 2e- η5-indenyl− 6e-
2μ-OH− 4e- SbR3 2e-
PR3 2e- CR22− 4e-
2 C 2H 4 4e- Total: 18e-
Total: 18e-
 Sabhuku Mudavanhu
HW # 1 – 2008 2

i) OsHCl2(N=Cy)(PR3)2 j) MoO2Cl2(κ2-MeSCH2CH2SMe)

Os(+4) d4 Mo(+6) d0
NR2− 4e- 2O2− 8e-
2Cl− 4e- 2Cl− 4e-
H− 2e- 2 SR2 4e-
N
2 PR3 4e- Total: 16e-
R3P H Total: 18e-
Os
Cl PR3
Cl
k) Ti(NR)(CH2Ph)2(κ3-1,3,5-triazacyclohexane) l) [Ru2(μ-Cl)3(η6-C6H6)2]+

Ti(+4) d0 Ru(+2) d6
NR2− 6e- η6-C6H6 6e-
2CR3− 4e- 3 μ-Cl− 6e-
3 NR3 6e- Total: 18e-
Total: 16e-

m) Cp*2Cr2(μ-CH3)2(C6F5)2 n) Rh(acac)(CO)2

Cr(+3) d3 Rh(+1) d8
Cp− 6e- acac− 4e-
C6F5− 2e- 2 CO 4e-
2 μ-CR3− 2e- Total: 16e-
Sub-total: 13e-
3 Cr-Cr 3e-
Total: 16e-

o) Ni(Ph)(CN)(dppe) p) Mo(CH3)5(OMe)

Ni(+2) d8 Mo(+6) d0
Ph− 2e- 5 CH3− 10e-
CN− 2e- OMe− 4e-
2 PR3 4e- Total: 14e-
Total: 16e-

q) CpFe(CN)(CO)2 r) TpTi(κ2-Tp)(S-S) (Tp = trispyrazoleborate)

R
Fe(+2) d6 Ti(+4) d0
B
Cp− 6e- S22− 4e-
CN− 2e- N Tp− 6e-
2 CO 4e- N N κ2-Tp− 4e-
Total: 18e- Ti Total: 14e-
S N

S N
B R

N
 Sabhuku Mudavanhu
HW # 1 – 2008 3

2. (12 pts) Propose an 18e- structure for the following metal/ligand combinations. Use at least one of each
metal and ligand listed. Complexes must be neutral. Don’t use more than 2 metal centers. Clearly show your
electron counting. Ligands are shown without charges, please indicate the proper ligand charge in your electron
counting. Draw a reasonable structure showing the geometry about the metal center(s).

a) Os, norbornadiene, Cl, pyridine b) Rh, Cp, Cl

Os(+2) d6 Rh(+3) d6
2 Cl− 4e- Cp− 6e-
2 pyridine 4e- Cl− 2e-
nbd 4e- 2 μ-Cl− 4e-
N Os Total: 18e- Total: 18e-
Cl
N Cl

c) W, Cl, NR, RC≡CR d) Y, Cp, Cl, THF

W(+6) d0 Y(+3) d0
2 NR2− 12e- O 2 Cp− 12e-
2 Cl− 4e- Cl 2 μ-Cl− 4e-
Y Y
alkyne 2e- THF 2e-
Cl
Total: 18e- O Total: 18e-
 Sabhuku Mudavanhu

Organometallic Chemistry - 4571 ANSWER KEY

HW # 2 Due: March 15 (by Noon!), 2007
Check the box to the right if you want your graded homework to be placed out in the public rack outside Prof.
Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (20 pts) For each of the following pairs of metal complexes, circle the one that will have the highest CO
stretching frequency. Briefly discuss your reasoning for each case. The highest CO stretching frequency will be the
complex with the least amount of electron density
a) CpRe(CO)3 -or- Cp*Mn(PEt3)(CO)2 that can be π-backbonded to the CO ligands.

The Mn complex is more electron-rich and will have the lower CO stretching frequency since it has the stronger
donating Cp* (pentamethyl-Cp) and PEt3 ligands, along with one fewer electron-withdrawing CO ligand. These ligand
effects easily over-ride the higher electronegativity of the Mn center.

b) W(CH)Cl2(CH3)(PMe3)(CO) -or- Ta(NR)(CH3)(CO)2[P(OMe)3]2

The W complex is in the +6 oxidation state and is d0, while the Ta complex is in the +3 oxidation state and d2. Even
with strong donating ligands it is safe to generally assume that a d0 complex will have the highest CO stretching
frequency. So ALWAYS electron-count.

c) PtCl4(CO)2 -or- [PtBr3(CO)]−

This Pt complex is in the +4 (d6) state with 4 poorly donating chloride ligands and two CO groups. This means that the
Pt center should have a reasonably high positive charge and contracted orbitals leading to less π-backbonding to the
CO ligands. [PtBr3(CO)]−, on the other hand, has Pt in the +2 (d8) state with three somewhat more strongly donating
bromide ligands, a formal negative charge on the complex, and only one CO ligand.

d) [Co(CO)4]− -or- [V(CO)6]−

Page 5 of Carbonyls: νCO [Co(CO)4]− = 1890 cm−1, νCO [V(CO)6]− = 1860 cm−1. Important explaination: Co is
considerably more electronegative. V is in a very low oxidation state (-1, relative to usual +3 or +5) meaning that it is
very electron-rich. This more than compensates for the presence of two more CO ligands. Co is also in the -1
oxidation state, but this is closer to its norm of 0 to +3.

e) CoF3(CO)3 -or- Cp*Mo(NO)(CO)2

The fluorides are very poor σ-donors and hang on to most of their negative charge. This makes the Co fairly electron-
deficient and with a fair bit of the positive charge from its +3 oxidation state localized and contracting its orbitals, thus
minimizing the π-backbonding to the CO ligands. Cp* is a strong donating anionic ligand and Mo is a fair bit less
electronegative than Co. These two factors out-weigh the presence of the NO+ ligand.

2. (20 pts) For each of the following pairs of metal hydride complexes, circle the one that should have the
lowest pKa value. Briefly discuss your reasoning for each case.
a) Cp2Zr(H)(Br) -or- [CpMo(H)(CO)3]+ The lowest pKa represents the highest acidity and
the complex with the least amount of electron
density. The hydride ligand wants to donate more
The Mo complex has only one good Cp donor, three good π-
of its electron-pair making it more protic.
backbonding (electron-withdrawing) CO ligands, and a localized
positive charge on the metal. All these work together to make the hydride the most acidic.
 Sabhuku Mudavanhu
HW#2 (2007) – Answer Key 2

b) H2Ru(C≡NCH3)2(CO)2 -or- H2Ru(PMe3)2(CO)2

Everything is the same except for the :C≡NCH3 (isocyanide) and :PMe3 ligands (both neutral). The alkylated
phosphine is the stronger σ-donor (negligible π-acceptor), while the isocyanide is not as strong a σ donor and a better
π-acceptor (see homework assignment # 1). This makes the isocyanide complex less electron-rich and more acidic.

c) Cp2V[P(OCF3)3](H) -or- [Cp2W(H)]−

The V complex has poor σ-donating phosphites that will be fairly good π-acceptors with the electron-withdrawing CF3
groups. This will make it easier to dissociate a proton. If the W complex loses a proton it will be dianionic and too
electron-rich.

d) HRh(CO)(PCy3)2 -or- HCo(CO)(PMe3)2

The ligands are pretty similar with the PCy3 being a somewhat stronger σ-donator relative to PMe3. Co is more
electronegative than Rh and this also helps make the Co complex the more acidic.

e) [HOs(PMe3)(dmpe)2]+ -or- HRe(CF3)2(CO)2[P(OMe3)3]2

Poor donor ligands coupled with moderate (phosphite) and good π-acceptor (CO) ligands is more important here for
the Re complex than the positive charge on the Os complex which has strong phosphine donor ligands. Six ligands
can override a single charge.

4. (10 pts) Consider Cp2Rh2[μ-(CF3CCCF3)](CO)(CNR) shown on page 7 of the Alkene/Alkyne chapter.

The Rh-Rh bond distance is 2.67 Å strongly indicating the presence of a covalent bond between the two
rhodium atoms. (a) (5 pts) show the electron-counting for this complex including Rh oxidation state,
ligand charges, # of e- donated, etc. Only one Rh center needs to be counted since both the CO and
C≡NR ligands are neutral 2e- donors making the complex electronically symmetrical from an electron
counting viewpoint. (b) (5 pts) Why does the alkyne ligand orient parallel to the Rh-Rh bond? From an
organic hybridization and bonding viewpoint how should the “alkyne” be considered? Draw a simple
orbital picture showing how the filled “alkyne” orbitals are overlapping with the empty Rh orbitals (use
the diagram below as a starting point, ignore all other ligands).

a) The electron-withdrawing groups on the alkyne allow it to oxidize each Rh center Rh(+2) d7
by 1e- to put each into the +2 oxidation state (d7) and convert the alkyne into a Cp- 6e-
dianionic bridging alkene ligand. This is analogous to the alkene example on the [CF3C=CCF3]2- 2e-
first page of the alkene chapter where the electron-withdrawing cyano groups CO (or CNR) 2e-
allow it to formally oxidize the Pt center and make a σ-coodinated metallocyclo- Rh-Rh 1e-
propane complex. 18e-

b) The 2e- reduction of the alkyne changes the carbon hybridization from sp to sp2 (double bond like). Each carbon
center now has a sp2 hybrid orbital in the plane of the double bond with a lone-pair to bond to each Rh center. By
using these stronger σ-donating orbitals the “alkyne” ligand now must orient parallel to the Rh-Rh bond axis.
Remember that ligands with π-systems and σ-lone pairs generally prefer bonding to the metal via the σ-lone pairs.
 Sabhuku Mudavanhu
Organometallic Chemistry - 4571 ANSWER KEY
HW # 2 Due: March 13, 2008
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (18 pts) For each of the following pairs of metal complexes, circle the one that should have the highest
average carbonyl IR stretching frequency. What does this tell you about the relative electron density on
the metal center (electron-rich or deficient)? Briefly discuss your reasoning for each case.
The highest CO stretching frequency corresponds to the metal that is the
a) [Rh(CO)4] -or- [Fe(CO)4]2 most electron deficient (poor) or has no d-electrons.

Rh and Fe have similar electronegativities and the same # of CO ligands. But Fe is in the 2 oxidation state and has
an overall 2 charge which makes it more electron-rich than the mono-anionic Rh complex. On page 5 of your
Carbonyl chapter notes the table at the bottom lists [Fe(CO)4]2 as having a rather low CO of 1790 cm1, while
[Co(CO)4] has a CO of 1890 cm 1.

b) [Re(PMe3)(N≡CMe)(CO)4]+ -or- [Mn{P(OPh)3}2(CO)4]

Both complexes are cationic and have the same # of CO ligands, but the phosphite ligands in the Mn complex are
poorer donors than PMe3 (about the same as N=CMe) and certainly better -acceptors making the Mn center more
electron-deficient. Mn is also more electronegative than Re and will hang onto it’s electrons a little more strongly have
have less tendency to -backbond to the CO’s.

c) CpFe(Br)(CO)2 -or- Os(C-Me)(O)(CH3)3(CO)

The Os complex is d0 (+8 oxidation state) and can’t p-backbond effectively to the CO ligands. The Fe complex is d6
and can.

d) Cp*Mn(PPh3)(CO)2 -or- CpIr(CO)2 (Cp* = C5Me5)

The Ir complex is more electron-deficient due to the less donating Cp ligand (compared to the stronger donating Cp*).
The Mn complex also has an extra donating (moderately) PPh3 ligand.

e) [Re(dmpe)2(PMe3)(CO)]+ -or- Ni(CO)3{P(OMe)3}

Although the Re complex is cationic, it has two sets of strongly donating alkylated dmpe ligands (the equivalent of 4
PMe3 ligands) and a PMe3 ligand and only one -backbonding CO ligand. These strongly donating ligands more than
compensate for the cationic charge on the Re making it more electron-rich. The Ni complex on the other hand is more
electronegative and has 3 CO ligands and one poorly donating (and moderately -accepting) phosphite ligand.

f) AuI(CO) -or- V(O)(CH3)(dppe)(CO)2

The Au complex is considerably more electronegative and will not want to -backbond well to the CO. The vanadium
complex on the other hand has a d2 configuration and some strongly donating ligands. As I mentioned during the
lectures on carbonyls, the tendency for metals to bind CO ligands drops off as one moves to the far right of the
transition metal series.
 Sabhuku Mudavanhu
HW#2 2008 2

2. (18 pts) For each of the following pairs of metal hydride complexes, circle the one that should have the
lowest pKa value. Briefly discuss your reasoning for each case.
The lowest pKa value refers to the most acidic hydride, which is the
a) HRe(CO)3(PPh3)2 -or- HRe(CO)3(dmpe) most electron deficient (poor) metal complex.

The dmpe ligand is considerably more donating than the two PPh 3 ligands. Therefore, the circled complex will be the
least electron-rich (most electron-deficient) and have the most acidic hydride (lowest pKa)

b) Cp2Ti(Br)(H) -or- HCo(CO)4

The cobalt complex has 4 electron-withdrawing (-backbonding) CO ligands that will drain electron-density from the
hydride and make the hydride more acidic. The Ti complex may be d0, but has good donating ligands making the Ti
center relatively electron-rich (though still unsaturated). The HCo(CO)4 complex was also clearly discussed multiple
times in class and in the notes as being a strong acid.

c) [HRu(N≡CMe)(CO)4]+ -or- HCo(CO)(PEt3)3

The three strongly donating PEt3 ligands make the Co center quite electron-rich, which will in turn make the hydride
more hydridic (less protic, less acidic, higher pKa). The Ru complex, on the other hand, is cationic and only has one
weakly to moderately donating acetonitrile ligand and 4 electron-withdrawing CO ligands. This will definitely make the
Ru complex the most acidic complex. The lower electronegativity and somewhat stronger second-row M-ligand
bonding effects are minor compared to the ligand and charge factors in this case.

d) TpOs(H)(CO)(NCCH3) -or- CpRu(H)(NCCH3)2 (Tp = tris(pyrazole)borate, see Lewis Base notes)

Tp is not as strongly donating as Cp and there is an extra electron-withdrawing CO ligand present on the Os complex.
These will work together to make the Os complex less electron-rich and the hydride more acidic. This will over-ride
stronger third-row metal-ligand bonding effect and lower electronegativity of the Os vs. Ru.

e) HRh(CO)(PCy3)2 -or- HIr(CO)(COD) (COD = cyclooctadiene)

The two PCy3 ligands are strongly donating and will make the Rh center more electron-rich and the hydride more
hydridic. The COD ligand is relatively weakly donating making the Ir less electron-rich and the hydride more hydridic.

f) HFe(NO)(CO)3 -or- Cp*2ZrH2

The strongly electron-withdrawing (-backbonding) NO+ and CO ligands will dramatically stabilize the anionic complex,
[Fe(NO)(CO)3] left after a proton dissociates. This will, therefore, be far and away the most acidic complex.
 Sabhuku Mudavanhu
HW#2 2008 3

3. (8 points) The nitrosyl ligand usually coordinates as a cationic ligand, NO+. It can, however,
occasionally act as an anionic NO ligand. When it is behaving as an anionic ligand it adopts a bent
coordination geometry. Discuss (using Lewis dot-like figures) the distribution of electrons in both kinds
of M-NO complexes and how these affect the structures (linear vs. bent). Assume in both cases that you
are dealing with a [M-NO]+ unit (positive charge on the overall complex) where the metal has 2 or more
d electrons. Clearly show the relative oxidation states of the metal and the relative d electron count for
each bonding case (linear vs. bent). I mentioned briefly in class that in some ways NO is the extreme
case of NO+ acting as a hyper -backbonding ligand. Explain what I meant by that statement.

NO+ is isoelectronic with CO, that is, it has the same bonding and electronic structure. The difference is that the
more electronegative nitrogen atom combined with the net positive charge work together to make NO + the
strongest -backbonding ligand known. In fact, it can backbond enough to formally oxidize the metal center by two
electrons to transform the NO+ ligand into a NO ligand. This is shown below in the transfer of a pair of electrons
from the metal to the NO+ ligand to
produce the bent NO ligand. The lone M(0) d6 M(+2) d4
pair that used to be on the metal center is
now on the nitrogen of the NO ligand.
M N O M N
This is what I was referring to as hyper--
backbonding. When the NO+ ligand turns O
into a NO ligand it has formally oxidized + 
the metal center by 2 electrons. That
NO NO
represents the “ultimate” in -backbonding.

4. (6 points) Circle the correct ordering of the following group of Fisher carbenes from the strongest
M=CR2 bond to weakest. Explain your reasoning.

Me2N NMe2 Me H Ph H MeO NMe2

a) b) c) d)
OC CO OC PMe3 OC CO OC CO
Cr Mo Cr W
OC CO OC PMe3 OC PMe2 Cl NO
C C
O PMe3 Me2P O

a>b>c>d b>c>d>a d>c>b>a c>a>d>b

b) has the strongest carbene bond because it has the poorest -donating groups on the carbene carbon atom – this
will allow the empty p-orbital on the carbene to be fully available to -backbond to the filled d-orbitals on the metal.
The Mo center is also the most electron-rich due to the strong donating alkylated phosphine ligands and the lower
electronegativity of the Mo center. The Cr center in c) also has strong donating phosphine ligands, but the Cr is a little
more electronegative than the Mo and can hang onto its electrons better and not -backbond as much. The Mo center
also has the second-row stronger M-L bonding effect to help it. The Cr complex c) also has a phenyl group on the
carbene carbon that can -donate to the empty p-orbital and weaken the ability of the carbene to -backbond to the
metal center. d) has the next weakest carbene-M bonding due to the strong -donating OMe and NMe2 groups on the
carbene filling up that empty p-orbital and the very strong -backbonding of the NO+ ligand that drains electron-density
off the W atom. a) has the very weakest M-carbene bond due to the two strong -donating NMe2 groups on the
carbene and the lack of any good donor groups on the metal.
 Sabhuku Mudavanhu
Organometallic Chemistry - 4571 Answer Key
HW # 3 Due: April 19 (by Noon), 2007
Check the box to the right if you want your graded homework to be placed out in the public rack outside Prof.
Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (30 pts) Identify the following reactions by their type (migratory insertion, elimination, β-hydride
elimination, oxidative addition, reductive elimination, ligand addition, ligand dissociation, ligand
coordination change, etc.). Note that in some cases you will have to use more than one description for a
reaction that has several steps. Note also that the order may be important! No discussion is needed.

a) CpIrCl(η3-allyl) + PMe3 CpIrCl(PMe3)(η1-allyl)

1. Ligand coordination change (η3-allyl to η1-allyl)

2. PMe3 ligand addition.

b) CpRh(CO)2 + CF3CF2Br CpRh(CO)(CF2CF3)Br + CO

1. oxidative addition to produce [CpRh(CO)2(CF2CF3)]+ (18e-) + Br−

2. CO ligand dissociation (favored by higher oxidation state and cationic charge on Rh)
3. bromide ligand addition

c) H2Rh(PPh3)2(Cl)(CH2CH3) HRh(PPh3)2(Cl) + CH3CH3

reduction elimination of H and CH2CH3
- or –
1. PPh3 ligand dissociation (makes 16e- metal that is more likely to reductively eliminate)
2. reduction elimination of H and CH2CH3
3. PPh3 ligand addition
O
d) CpFe(CO)2(Me) + PPh3 CpFe(CO)(acyl)(PPh3) (acyl = C )
CH3
1. migratory insertion of CO and Me ligands to make acyl
2. PPh3 ligand addition

e) PtCl2(CH2CH3)2(PMe3)2 PtCl2(PMe3)2 + CH2=CH2 + CH3CH3

1. Cl− ligand dissociation (must make empty orbital for β-hydride elimination, Cl− is weakest binding ligand)
2. β-hydride elimination to make Pt-H(ethylene) complex
3. CH2=CH2 ligand dissociation
4. reduction elimination of H and CH2CH3 (steps 3 and 4 in either order)
5. Cl− ligand addition

f) [Cp2Mo(H)(CH2=CH2)]+ + PPh3 [Cp2Mo(CH2CH3)(PPh3)]+

1. migratory insertion of H and ethylene ligand to make Mo-CH2CH3

2. PPh3 ligand addition
 Sabhuku Mudavanhu
Organometallics Homework #3 (2007) – ANSWERS 2

2. (20 pts) For each pair of complexes shown below, circle the one that should be the most reactive towards
the oxidative addition the substrate shown. Give a brief but clear explanation for your choice.
We are looking for the most electron-rich complex that has an empty orbital and at least 2 d electrons.
For non-electrophillic reactants we also need an empty orbital to pre-coordinate the reactant.

a) [Co(dmpe)2]+ -or- [Rh(dppe)2]+ Substrate = H2

The dmpe ligands are considerably stronger donors compared to dppe, so the Co complex will be easier to oxidize.
This over-rides the higher electronegativity of the Co center. Both complexes have a 16e- count.

b) RhCl(PPh3)3 -or- RhCl(CO)(PPh3)2 Substrate = CH3CH2Br

Although the three PPh3 ligands make the first Rh complex more electron-rich, the steric bulk of the three PPh3
ligands is more important for the more sterically hindered CH3CH2Br substrate.

c) Co(CO)(PEt3)2Cl -or- Ir(CO)(PMe3)2Br Substrate = HSiMe3

The Ir is less electronegative and the Br− is a stronger donating ligand relative to Cl−. PEt3 is a slightly stronger
donating ligand, but this probably would not compensate for the bromide ligand and lower electronegativity of the Ir
center. Sterics is also important here due to the shorter Co-ligand bonds and the larger PEt3 ligand. Both complexes
have a 16 e- count.

d) Cr(CO)6 -or- W(CH)(CH3)3(dmpe) Substrate = CH3Cl

The W complex is d0 and can’t do an oxidative addition reaction. CH3Cl is an electrophillic substrate and does not
need an empty orbital on the Cr center.

3. (10 pts) (η3-allyl)Co[P(OMe)3]3 is an arene hydrogenation catalyst that can cleanly hydrogenate benzene
to cyclohexane.
a) (5 pts) It is known that the first reaction step in the hydrogenation mechanism is H2 oxidative addition to
the complex. It is also known that there is no phosphine dissocation for this step. How does H2 add to
the complex? Discuss.

The η3-allyl ligand changes its coordination mode from η3 to η1, and this opens up an empty orbital to
allow the H2 to bind and do the oxidative addition.
 Sabhuku Mudavanhu
Organometallics Homework #3 (2007) – ANSWERS 3

b) (5 pts) The use of bulkier phosphite ligands such as P(OEt)3 or P(OiPr)3 speeds up the rate of arene
hydrogenation. Discuss the reason(s) for this observation. The statement in part a) does not necessarily
apply.

Two good reasons (either will do):

1) The bulkier phosphites can dissociate more easily due to increased steric hindrance. This opens up
a coordination site to allow the arene substrate to bind and start the hydrogenation. Remember that
phosphites do not bind that strongly.

2) The bulkier phosphite ligand cause more steric hindrance, which favors and speeds up the η3- to η1-
allyl coordination mode change. The faster this occurs the faster the reaction of H2 with the catalyst.

4. (20 pts) Consider the following reactions. Sketch out the final product clearly showing the structure and
geometry. The rxn steps listed may not be in the correct order. If they are NOT in the correct order
please include a brief and clear explanation of the correct order of steps and why they go in that order.

a) [Fe(CO)4]2− + CH3Br (oxidative addition) CH 3 Br −

2- Charge balance!! If you start with a dianionic complex the negative charges O
O C
can’t simply go away!! The Fe(2-) center is oxidized by two electrons to make Fe C O
C H an Fe(0) center with an anionic CH3 ligand (overall negative charge). The other
O C Fe C Br
negative charge goes to the bromide anion that does not coordinate to the 18e- C Fe(0)
[Fe(CH3)(CO)4]- complex. Many of you put down Fe(CH3)(Br)(CO)4 as your O
Fe(2-) C
H answer. This is an Fe(2+) complex which represents a 4e- oxidation of the
C d8
d
10 C H

18e-
O metal center and loss of the dianionic charge. O 18e-
O

b) [Ru(PMe3)(CO)4(acyl)]+ (elimination, ligand dissociation)

O
O CH3 O CH3
C C C
O O O O
C C - CO C C CH 3
Ru Ru Ru
C PMe3 C PMe3 C PMe3
O C O C O C
O 18e- O 16e- O 18e-
Ligand dissociation has to be the first step in order to make an empty orbitial cisoidal to the acyl group for the
carbonyl elimination.
c) Ir(CH3)2Cl(dmpe) + N≡CCH3 (reductive elimination, ligand addition)
CH3
Me 2 - CH 3CH3 Me2 N CMe Me2
H3C P P MeC N P
Ir Ir Ir
Cl P Cl P Cl P
Me2 Me2 Me2
Ir(+3), 16e- Ir(+1), 14e- Ir(+1), 16e-
Reductive elimination is OK as a first step due to the unsaturation of the Ir(+3) complex.
d) CpMo(H)(CH2=CHCH3)(dmpe) + 2CO (2 migratory insertions, 2 ligand additions)
1. migrat ory
migratory inser tion
insertion + CO 2. +CO
Mo Mo Mo Mo
H PR2 PR 2 O C PR 2 O C PR 2
R 2P R2P R2P R2P
Pr
O
Steps shown above.
 Sabhuku Mudavanhu
Organometallics Homework #3 (2007) – ANSWERS 4

5. (20 pts) Shown below is a catalytic cycle for the cyclocoupling of CO2 and diynes developed by Prof.
Janis Louie at the University of Utah (JACS, 2002, 124, 15188).
a) (15 pts) Label the steps with boxes next to them. There may be more than one step shown in each
transformation. IPr ligand shown below.

Ni(0), 12e-
O + CO 2
O Ni(IPr)

reductive
elimination IPr
Ni
O Ni(0), 16e-
C
Ni(+2), 16e- Ni(IPr) O
O
O IPr
Ni
migratory O
1. oxidative coupling
2. alkyne ligand addition
insertion O
Ni(+2), 16e-

N N
..

IPr
b) (5 pts) The ligand is shown as a neutral ligand and Prof. Louie draws the bond from the IPr to the Ni as a
single bond. Is this correct? Clearly discuss.

The Ni complex is a late transition metal carbene that should act as a Fisher carbene, which one typically considers as
a neutral 2e- donor. The empty carbene p-orbital is not going to do much π-backbonding to the metal due to the
presence of the two strongly π-donating N atoms flanking the carbene carbon. As was discussed in the notes the
more π-donating the organic groups next to the carbene carbon, the less π-backbonding to the metal center. This
effectively makes the carbene to Ni bond a single bond. See the “Hot New Carbene” ligand discussion in your Alkyl
Chapter page 14.
 Sabhuku Mudavanhu

Organometallic Chemistry - 4571 ANSWER KEY

HW # 3 Due: April 10, 2008

Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (30 pts) Predict and sketch out the structure for the transition-metal containing product for the following
substitution reactions using one equivalent of each the reactants. State whether the mechanism is most
likely associative or dissociative and reason(s) for your choice.
a) CpFe(CH3)(CO)(H2C=CHCH3) + PPh3
Dissociative: The Fe complex is 18e-, so it needs to lose the weakest
coordinated ligand to open up a coordination site to bind the new ligand.
Propylene will definitely be the most labile ligand.

b) ReCl(CO)3(PMe3)2 + CH3−
Dissociative: The Re complex is 18e-, so it needs to lose the weakest
coordinated ligand to open up a coordination site to bind the new ligand.
Chloride is the most likely candidate to dissociate first.

c) RuCl2(dmpe)(CO) + Br−
Associative: The Ru complex is 16e-, so it already has an empty orbital and has
fairly small ligands to allow an associative substitution by bromide to replace one
of the more weakly bound chloride ligands. Ru has a moderate tendency for 16e-
d 6 complexes.

d) W(CO)2(PEt3)4 + P(OMe)3
Dissociative: The W complex is 18e-, so it needs to lose the weakest coordinated
ligand to open up a coordination site to bind the new ligand. Since the CO’s are very
strongly π-backbonding, one of the bulkier, electron-donating PEt3 ligands should
dissociate first. 4-strongly donating alkylated phosphine ligands makes the metal too
electron-rich so this (and sterics) will favor PEt3 dissociation to allow a poorer σ-donor,
better π-acceptor, and smaller phosphite ligand to coordinate.

e) [Rh(CO)2(PPhMe2)2]+ + PEt3
Associative or dissociative: The Rh complex is 16e-, so it
has an empty orbital to allow an associative substitution by
PEt3 to replace one of the other ligands. But if you judge the
PPhMe2 ligands as being too bulky, proposing the dissociation
of one of them is reasonable. Alternatively, the cationic charge
will favor dissociation of one of the CO ligands over the
electron-donating phosphine. So that would be a reasonable choice. So this can lead to two reasonable
possible substitution products.

f) CpTa(=CH2)(CH3)(κ2-CF3NCF2CH2N(CH3)2) + CH2CHCH2− (allyl)

Associative: The Ta complex is 16e- (counting the amide as a 2e- donor) so it has an empty
orbital and has fairly small ligands to allow an associative substitution by allyl to replace the
more weakly chelating amine-amide ligand. The electron-withdrawing CF3- and CF2-groups
on the amide nitrogen will weaken its donor ability considerably, favoring complete substitution
by the stronger donor allyl. The η3-coordination mode is the most common for allyl.
 Sabhuku Mudavanhu
HW # 3 (2008) 2

2. (25 pts) Circle the ligand on the following complexes that will most easily dissociate. Briefly state the
reason(s) for your choice.
a) b) (R = alkyl groups)

The two acceptable choices are Br− and N≡CMe

(acetonitrile). The negative charge on the complex The antimony ligand coordinates the weakest due to
makes dissociation by a halide somewhat easier. the poor σ-orbital overlap efficiency (large diffuse lone
On the other hand, acetonitrile is a neutral ligand pair orbital on the Sb) and the lower energy (poor
and typically doesn’t coordinate too strongly. donor ability) of the lone pair orbital. The hapticity
changing ability of the indenyl ligand does not play a
role here. The N-heterocyclic carbene ligand is a very
strong donor and very unlikely to dissociate.
c) d)

The terminal chloride is the weakest ligand and the My first choice would be the CO ligand, since an
easiest to dissociate. A bridging chloride ligand is anionic cyanide is a fairly strong σ-donor (and usually
bonding to two metal centers and has to break both a poor π-acceptor). But I will accept the reasoning that
bonds before dissociating, which is usually harder
the CO ligands are π-backbonding strongly enough to
to do relative to a terminal ligand.
make the cyanide more likely to dissociate.
e) (R = Ph) f) (R = Me)

Pd O
R3P O S CF3
O
The dppe ligand is not that strong a coordinating The SO2CF3 group is very electron-withdrawing,
ligand, even with the chelate effect. Both Ph− and making the anionic oxygen a very poor donor,
CN− are considerably stronger σ-donors and will especially for late transition metals that aren’t
help to labilize (weaken) the dppe ligand for oxophillic in the first place. This group is called a
dissociation. For example, cyanide is used by my trilate anion and is considered a non-coordinating
group to displace alkylated phosphines from anion due to its very weak bonding interactions with
transition metal centers. most metal centers.

3. (10 pts) Re(O)(CO)4[P(OMe)3] reacts extremely quickly with one equivalent of PMe3 to do a CO ligand
substitution. Mn(OMe)(CO)3(dmpe), however, reacts far more slowly with PMe3 to do a CO ligand
substitution. Clearly state the reason(s) for this.
Re(O)(CO)4[P(OMe)3] is a 19e- complex and the one extra electron is in a metal-ligand antibonding orbital that will
favor dissociation by one of the existing ligands. CO substitution is favored in order to give stronger π-backbonding for
the remaining CO ligands after substitution. [I actually wanted this to be a 17e- system, but put one too many CO
ligands on the complex, but the answer is the same either way]
Mn(OMe)(CO)3(dmpe) is 18e- and has a good balance of σ-donating and π-backbonding ligands. This more than
compensates for the “third row” stronger M-L bonding effect.
 Sabhuku Mudavanhu
HW # 3 (2008) 3

4. (15 pts) Consider the following allyl-mediated substitution reaction:

η3-η1 hapticity change 1) CO dissociation

PMe3 ligand addition
2) η1-η3 hapticity change

a) (8 pts) Label each forward-going reaction step in the boxes provided below the reaction (there may be
more than one fundamental reaction occurring in each setp, if so, label in the correct order).
b) (7 pts) Of the last two compounds, the final product is the most stable. Clearly state the reason(s) for
this.
The anionic η3-allyl ligand (and PMe3) donates more electron-density to the Mn atom making it more
electron-rich so it can engage in more π-backbonding to the 3 remaining CO ligands. This is a more
stable situation than 4 CO ligands competing for π-backbonding with an η1-allyl and one PMe3 ligand.

5. (20 pts) To which of the following intact (no ligand dissociations) complexes can H2 do an oxidative
addition reaction to make a dihydride complex. Please circle Yes or No for each complex and clearly state
the reason(s) for this.
You need at least a d2 metal center and an empty orbital (17e- or lower) for H2 to be able to coordinate
and do an oxidative addition.
a) Cp2Ti(CO)2 Yes  -or- No b) Cr(CH)(CH3)2(dppe) Yes  -or- No

18e- Ti(+2) d2 complex with no empty orbitals 15e- Cr(+5) d1 complex, not enough d electrons for
a 2e- oxidative addition.

c) CpFeCl(PPh3) Yes  -or- No d) Pt(PPh3)3 Yes  -or- No

16e- Fe(+2) d6 complex; OK for H2 oxidative 16e- Pt(0) d10 complex; OK for H2 oxidative
addition addition. Note that d10 Pt is very different from a
square-planar d8 Pt(+2) center.

e) [Rh(CO)2(PMe3)3]+ Yes  -or- No

18e- Rh(+1) d8 center with no empty orbitals (CO

ligands, however, are probably quite labile due to
the cationic charge).
 Sabhuku Mudavanhu
Organometallic Chemistry - 4571 ANSWER KEY
Homework # 4 -- Due: May 1, 2007
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (20 pts) Write out a catalytic cycle for the hydrophenylation of alkenes to produce alkylated arenes:
R

R + +

The starting catalyst is shown below and you are to use benzene as the arene and ethylene (ethene) as the
alkene. The catalysis proceeds by the following reaction steps: 1) arene C-H oxidative addition, 2) alkene
addition, 3) migratory insertion, 4) reductive elimination. The exact ligands involved in step 3 is not specified,
you are to choose the most likely ligands to do this reaction. Ligand dissociation of the initial ligands is
allowed if necessary, but I have not indicated when this may (or may not) happen. Clearly sketch out each
metal complex with proper geometries. [Periana et al., JACS, 2000, 122, 7414-7415]

Ir(acac)(η4-benzene)

+ benzene ligand addition

O
Ir
O

oxidative addition
reductive reductive + benzene
elimination elimination ligand addition

O O O
Ir Ir Ir
O H O O H

migratory ligand addition

insertion

O
Ir
O H

Note that there are two possible migratory insertions and both are acceptable and of similar likelihood. I have a moderate
preference for the migratory insertion of the alkene and hydride due to easier movement of the hydride and its spherically
symmetrical s orbital that can overlap well with the alkene. The phenyl ring, however, also has a π-system “sticking out”
that can also overlap reasonably well with the alkene to do the migratory insertion.
 Sabhuku Mudavanhu
HW # 4 – 2007 Answers 2

Read the attached paper from the Journal of the American Chemical Society and answer the following questions
about it.

2. (10 pts) The catalyst precursor used is listed as [RhCl(coe)2]2. What is coe? Sketch out the structure of
[RhCl(coe)2]2 – you can abbreviate the coe ligand as:

cyclooctene
coe = ______________________
Cl no Rh-Rh bonding due to d 8
traditionally [RhCl(coe)2]2 is not written out Rh Rh square planar configuration
Cl that is happy with 16e- count
as Rh2(μ-Cl)2(coe)4 because it falls apart quite
easily to make reactive 14e- monometallic
complexes.

3. (15 pts) From Table 2 calculate the following:

10 (2 Rh centers, see note below)

a) maxium # of turnovers (TON): _______

0.42 hr−1
b) average turnover frequency (TOF hr−1) for entry # 1 (assume 85% conversion to product) = ________

1.23 hr−1
c) using the last catalytic run from Table 1, calculate the average TOF for this run = ________

a) 5 mole % catalyst refers to the amount of catalyst precursor relative to the amount of reactant (substrate). So if one
has 1 mole (or equivalent) of reactant then there is 0.05 moles (or equivalents) of catalyst precursor. # of TO = 1/0.05
= 20 TO. BUT, each catalyst precursor has TWO Rh centers and falls apart to generate TWO monometallic catalyst
complexes. Thus the 5 mole % is actually 10 mole % on a Rh basis. The authors MIGHT have accounted for this in
their catalyst mole % figure, so we will accept 10 or 20 as the answer. If so this will also double the answers listed for
b) and c).
c) the yield was 86% with 10 mole % catalyst (but 2 Rh equivalents), so there were 4.3 TO’s over 3.5 hours
(TOF = 4.3/3.5 hr = 1.23 hr−1)

4. (10 pts) In the scheme on the first page, column 2, substrate 1 can be isomerized to 2 or 3. Clearly, 1 can be
converted to the product 4. Can 2 or 3 directly cyclize to form 4? Explain your answer for 2 and 3.
2
1
3 4
YES, substrate # 2 can ring close to form the desired product 4. So long as there is a
N double bond at carbon 3, this carbon atom will have the reactivity to ultimately do the
ring closing to form product 4.

N 2

2
1
3 4
NO, substrate # 3 does NOT have double bond character at carbon 3 needed to
N perform the eventual ring closing. Carbon 2 might be able to couple, but this
would form a 4-membered (and more strained) ring system that is NOT product
X

4.
N
3
 Sabhuku Mudavanhu
HW # 4 – 2007 Answers 3

5. (25 pts) Sketch out a catalytic cycle for 1 being converted to 4 (no isomerization). You only have to draw
the imidazole ring and N-alkenyl group on 1. Start with the catalyst shown below. The first step is
coordination of 1 via the less substituted N lone pair. The second step is C-H bond activation (but label this
with the more correct mechanistic term) of the adjacent C-H bond. Based on this information, complete the
cycle. Clearly label each step with what is mechanistically happening.

ligand Cy 3P O
addition Rh
O Cl O
N

ligand substitution
N

reductive elimination
Cl Cy 3P O
Cy 3 P O Rh
Rh N Cl N
N
N H

migratory
insertion oxidative addition

Cl Cl
Cy 3P O Cy3 P O
Rh N Rh N
H H
N alkene N
ligand addition

The oxidative addition of the C-H bond to the Rh breaks the weaker Rh-N bond to generate the 16e- Rh(+3) complex.
After the alkene ligand adds, the migratory insertion must proceed to give the branched alkyl product with the 6-
membered “chelate” ring. The somewhat more stable 6-membered ring system formed, relative to the 7-membered ring
that would form if the migratory insertion went the other way, is probably the driving force for this.
 Sabhuku Mudavanhu
HW # 4 – 2007 Answers 4

6. (10 pts) At what point in the catalytic cycle is the alkene isomerization discussed in question # 4 (and the
paper) most likely to happen. Sketch out the isomerization of 1 to 2 and label each step (once again, you
don’t have to draw out the arene ring on 1 and 2).

Cl Cl Cl
Cy 3 P β-hydride Cy 3P
Cy 3P O O O
elimination
Rh Rh N Rh N
N
H H
N N N

The alkene is isomerized by performing a β-hydride elimination from the circled carbon atom in the middle structure
shown above. This moves or isomerizes the double bond. This is clearly happening as a side reaction in the catalysis
since the authors do report the formation of 2 and traces of 3. Isomer 3 is more difficult to make since this involves
forming a somewhat more strained 5-membered ring and doing the proper β-hydride elimination from that.

7. (5 pts) Given the catalytic conditions (temp, catalyst loading, TOF), do you think the following similar
reaction is likely to be catalyzed by the best catalyst discussed in this paper? Fully discuss.
CH 3 CH 3 The coupling reaction of ethylene
and imidazole should be much slower
N N and more difficult to do relative
to the "linked" reactant N
+
molecules that the authors
N N used in this paper. N
The tethering of the alkene group onto the imidazole substantially increases the odds (kinetic probability) of it reacting
with the metal center in the short period of time that the imidazole ring has oxidatively added to the Rh center.
Remember that the reverse alkyl-hydride reductive elimination reaction to kick off the free imidazole can and is
happening all the time, otherwise the authors could observe the carbon-bound imidazole C-H oxidative addition
product via NMR. Attaching a reactive group onto the substrate makes it a lot easier to coordinate to the metal and
this is analogous to the chelate effect that we have discussed many times in class. So the above reaction should go
much more slowly.

8. (5 pts) The authors add some excess PCy3, but I’ve only drawn the catalyst with one PCy3 ligand. Why
didn’t I use two PCy3 ligands on the catalyst?

Two PCy3 ligands would make the catalyst way too sterically hindered to do this reaction. It is typical to add a little
extra phosphine ligand to maintain at least one coordinated phosphine ligand which generates the active catalyst. At
the rather high reaction temperature of 160-180 ºC (fairly high for a homogeneous catalyst) there will be a fair bit of
phosphine ligand dissociation, even for a strongly donating alkylated phosphine ligand like PCy3. Adding some excess
phosphine ligand will help push the equilibrium back towards the mono-phosphine Rh complex.
 Sabhuku Mudavanhu

Organometallic Chemistry - 4571 ANSWER KEY

Homework # 4
Due: Tuesday, April 29, 2008
Check the box to the right if you want your graded homework to be placed out in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick up your homework from Prof. Stanley in person:

1. (20 pts) Starting with the catalyst shown below (and the first step) sketch out the catalytic cycle for the
trimerization of ethylene to make 1-hexene. Clearly label each step.

Cr(+3), d3, 11e-

Ph2
Cl
P
N Cr
P
Ph2 Cl 2 2 ligand additions
reductive
elimination

Cl H Cl
Ph2
Cr(+5), d1, 15e- Ph2
P
N
P
N Cr Cr(+3), d3, 15e-
Cr
P P
Ph2 Cl Ph2 Cl

oxidative coupling
-hydride -or-
elimination oxidative addition

Ph2
Cl Ph2
Cl
P P
Cr(+5), d1, 13e-
N Cr N Cr Cr(+5), d1, 13e-
P P
Ph2 Cl Ph2 Cl

ligand addition
migratory insertion

Cl
Ph2
P
N Cr Cr(+5), d1, 15e-
P
Ph2 Cl
 Sabhuku Mudavanhu
Organometallics HW # 4 (2008) 2

Read the attached paper from the Journal of the American Chemical Society (Shirakura & Suginome, 2008,
130, 5410-5411) and answer the following questions about it.

2. (10 pts) What is the likely nickel catalyst (what the authors refer to as Ni(0)Ln) that initially reacts with the
alkyne? Sketch out this species and indicate its overall electron-count and d-electron count. Use the
phosphine ligand that the authors report works best for this catalyst. Briefly discuss why did you chose this
compound?
This is the catalyst species that reacts with a H-C(≡C) bond to do the initial
oxidative addition reaction. A H-C bond is non-electrophillic and requires an empty
orbital on the metal in order to initially coordinate before the oxidative addition
actually occurs. Ni(PBu3)3 is a Ni(0), d10, 16e- species that has an empty
coordination site for this. Ni(PBu3)4, on the other hand, is an 18e- species that must first lose a phosphine
ligand in order to open up an empty coordination site. Ni(PR3)4 would be considered the catalyst
precursor. Electronically, the Ni(0) d10 center should not want 4 strongly donating alkylated phosphine
donors and will favor dissociation of one to make the more reactive 3-coordinate tris-phosphine compound.
The authors add 4 equivalents of PBu3 to make sure the Ni centers doesn’t become too unsaturated and
start decomposing or precipitating metallic nickel. A Ni(PBu3)2-type complex doesn’t have enough good
donors and too low an electron-count (14 e-) to favor the oxidative addition step.

3. (10 pts) From Table 1 calculate the following for entry # 11 (assume 100% conversion to product):

a) # of turnovers (TON): _______

10 (10 mole% catalyst = 10 turnovers)

b) average turnover frequency (TOF, hr−1) = ________

2.5 hr-1 (10 turnovers/4 hours)

4. (10 pts) Why doesn’t’ P(OBu)3 work as a ligand for this catalytic reaction relative to PBu3?

P(OBu)3 is a phosphite ligand and a fairly poor σ-donor and moderately good π-acceptor ligand. The PBu3
ligand, on the other hand, is an alkylated phosphine and a very strong σ-donor and poor π-acceptor ligand.
This will make the metal center electron-rich enough to favor the H-C(≡C) bond oxidative addition. A
secondary reason could be the favorable loss of a PBu3 ligand from Ni(PR3)4 that will generate the active
Ni(PBu3)3 catalyst for the electronic reasons discussed above (see page 4 in Ligand Substitutions and the
quiz question asked in class about the electronic factors involved in Ni(PR3)4 complexes).

5. (20 pts) Label the lettered steps in the authors proposed catalytic cycle (all steps proceeding clockwise). If
there is more than one step, list them in the correct order.

A= 1) PR3 ligand dissociation (if you think it is NiP4)

2) oxidative addition (of alkyne C-H bond)

A
1) PR3 ligand dissociation (to give 16e- complex)
B= 2) ligand addition (of one diene double bond)
C 3) migratory insertion (of Ni-H and alkene)
4) η1 to η3-allyl hapticity change

C= 1) η3 to η1-allyl hapticity change

2) reductive elimination (of alkynyl and η1-allyl)
3) PR3 ligand addition (to regenerate NiP3 catalyst)
B
 Sabhuku Mudavanhu
Organometallics HW # 4 (2008) 3

EXTRA: Shown below is my full proposed catalytic cycle for the abbreviated one shown above.

Notes:
The hydride and anionic alkynyl ligands are about equally likely to do the migratory insertion reaction, but
you have to make sure that if you use the alkynyl ligand that you add it to the internal carbon atom of the
non-R-group substituted alkene. I used the hydride ligand in my mechanism (as did the authors). But the
two π-orbitals on the alkynyl ligand and good overlap with the alkene orbitals makes the alkynyl ligand
much better candidate for this relative to a simple alkyl group.
 Sabhuku Mudavanhu
Organometallics HW # 4 (2008) 4

6. (30 pts) Sketch out a catalytic cycle for the dimerization of two of the alkyne reactants to give the side
product 4a (SiMe3 group). Clearly label each reaction step and show the catalyst complex involved in each
step. Start with the catalyst complex shown below (no phosphine ligands involved in this cycle).

associative substitution SiMe3

& ligand addition SiMe3 16e-, d10
Ni H H
SiMe3
Me3Si H
SiMe3 SiMe3
+2 oxidative
addition
H
SiMe3
SiMe3
SiMe3 H
H Ni 16e-, d8
Ni H

H C
16e-, d10 SiMe3 C
(2e- & 4e- alkyne donors) SiMe3 SiMe3

reductive migratory
elimination insertion
H SiMe3

H
H 14e-, d8 (2e- alkyne donor)
Ni 16e-, d8 (4e- alkyne donor)

SiMe3 C
C
SiMe3
 Sabhuku Mudavanhu

Exams
for the last 2 years

Followed by Answer Keys

 Sabhuku Mudavanhu

CHEM 4571 – Organometallic Chemistry Name __________________________

EXAM # 1 – Feb 15, 2007 Signature _________________________

Check this box if you want your graded test put out
Please answer all questions! in the public boxes outside Prof. Stanley’s office:

1. (60 pts) Sketch out the structure of the following transition metal complexes as accurately as possible
and clearly show the electron counting (including the oxidation state of the metal center and ligand
charges if present). You don’t have to draw out phenyl rings on ligands (e.g., for PPh3).

a) [Co(CH3)3Cl3]3−

b) CpW(NO)(CO)(PR3)

c) [Rh2(μ-dppm)2(μ-Cl)(N≡CMe)2]+ (dppm = Ph2PCH2PPh2)

d) Cp2Ta(CCH3)

e) Cp2Co
 Sabhuku Mudavanhu
Exam # 1 (2007) 2

f) [AuCl2Ph2]− (Ph = C6H5)

g) V(NCH3)Cl3(dppe) (dppe = Ph2PCH2CH2PPh2)

h) Ir2(μ-OMe)2(H2C=CH2)4

i) Cp2Zr(NMe2)(η1-CH2CH=CH2)

j) [CpW(PR)(CO)3)]+

k) [Cr2(CH3)8]4−

l) V(CO)6
 Sabhuku Mudavanhu
Exam # 1 (2007) 3

2. (30 pts) For each of the following pairs of complexes, which will have the highest average CO infrared
stretching frequency? Circle your choice and briefly explain your reasoning.

a) Ni(CO)4 - or - [V(CO)6]−

b) CpNb(CR)Cl(CO) - or - CpV(CH3)2(CO)

c) Cr(CO)3(PMe3)3 - or - MnCl(CO)5

d) Cp2Zr(CO)2 - or - [RhCl2(CO)2[P(OMe)3]2]+

e) [Rh(CO)4]+ - or - [Ir(CH3)2(CO)2(PMe3)2]+

f) Mo(dmpe)2(CO)2 - or - W(dmpe)(CO)4 (dmpe = Me2PCH2CH2PMe2)

 Sabhuku Mudavanhu
Exam # 1 (2007) 4

3. (20 pts) Consider the isocyanide (C≡NR, sometimes called isonitrile) and nitrile (N≡CR) ligands that are
isomers of one another.
a) (10 pts) Sketch out a Lewis dot diagram for each showing the location of the lone pair(s) and any formal
charges based on organic valence conventions.

b) (5 pts) Which ligand is the better σ-donor? Why?

c) (5 pts) Which ligand is the better π-acceptor? Why?

4. (40 pts) Sketch out a neutral 18-electron structure showing the geometry about the metal center as
accurately as you can at this point in the course for the following metals and ligands. Use at least one
metal and each type of ligand shown. Try to keep your structure as simple as possible (bimetallic
complexes are OK, nothing higher). Clearly show your electron counting. Ligands are shown without
charges, please indicate the proper ligand charge and metal oxidation state in your electron counting.

a) Mo, μ-CR2, dmpe, CO b) Nb, NMe, NMe2, Cp, Cl

c) Ru, C6H6, H, PMe3 d) Mn, CH3, CO

 Sabhuku Mudavanhu

CHEM 4571 – Organometallic Chemistry Name: _________________________

EXAM # 1 – Feb 21, 2008 Signature: ________________________
Check the box to the right if you want your graded exam to be placed in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick it up from Prof. Stanley in person:

Please answer all questions!

1. (40 pts) Sketch out the structure of the following transition metal complexes as accurately as possible
and clearly show the electron counting for each including the metal oxidation state and ligand charges.
You don’t have to draw out phenyl rings on ligands (e.g., PPh3).

a) [Cr(PH2)(CO)5] 

b) Cp2Rh2(-NHMe)2

c) [ReCl(H2C=CH2)(dppe)2]+ [dppe = Ph2PCH2CH2PPh2]

d) CpY(NR2)(CH3)(THF) (THF = O )

e) CpMo(PMe3)2(CCMe)(CO)
 Sabhuku Mudavanhu
Exam # 1 (2008) 2

f) [trans-AuI2Ph2]  (Ph = C6H5)

g) V(NMe)Cl3(CH3OCH2CH2OCH3)

h) Ir2(-Br)2(CO)4

2. (40 pts) For each of the following pairs of complexes, which will have the lowest average CO infrared
stretching frequency? Circle your choice and briefly explain your reasoning.

a) CpFe(CO)2(PF3) -or- CpOs(CO)(PMe3)2

b) Cp2Y(CH3)(CO) -or- Cp2V(CH3)(CO)

c) Cr(CO)4(PEt3)2 -or- W(CO)4(PPh3)2

d) PtCl4(CO)2 -or- NiBr2(CO)2

 Sabhuku Mudavanhu
Exam # 1 (2008) 3

3. (30 points) a) (20 pts) Show the charges (may be 0) and number of electron pairs (may be zero) on the
donor atoms that will coordinate to the metal center for the following chelating ligands:

b) (10 pts) Order the ligands above from strongest to weakest donor for a Zr(+4) metal center and include
your reasoning. You can refer to the ligands by their primary donor atom type (e.g., S, O, N, etc) and do
not have to sketch them out.

4. (40 pts) Sketch out a neutral 18-electron structure showing the geometry about the metal center as
accurately as you can at this point in the course for the following metals and ligands. Use at least one
metal and each type of ligand shown. Try to keep your structure as simple as possible (bimetallic
complexes are OK, nothing higher). Show your electron counting. Ligands are shown without charges,
please indicate the proper ligand charge and metal oxidation state in your electron counting.

a) W, -PR2, CO, H b) Hf, Cp, NCCH3, NCH3

c) Pt, CH, Cl, PMe3 d) Nb, O, CH3, Cp, PMe3

Bonus (10 pts): Why is C≡NMe a weaker -acceptor than C≡O? There are two primary reasons.
 Sabhuku Mudavanhu
CHEM 4571 - Organometallic Chemistry Printed Name ______________________
EXAM # 2 - March 29, 2007 Signature__________________________
Check this box if you want your graded test put out
Please answer all questions! in the public boxes outside Prof. Stanley’s office:

1. (20 pts) Which of the following metal hydrides should be the most acidic? Clearly explain your reasoning.

a) HNb(CO)6 -or- HV(CO)5(PMe3)

b) HRh(CO)(PPh3)2 -or- HRh(CO)2[P(OPh)3]

c) [HOs(PMe3)(dmpe)2]+ -or- HRe(CF3)2(CO)2[P(OMe3)3]2

d) [HCoCl(NH3)4]+ -or- CpFe(H)(dppe)

2. (10 pts) a) (5 pts) Electron-count W(NMe2)6 clearly showing the W oxidation state, ligand charges, and #
of electrons donated from the ligands to the metal center.

b) (5 pts) Based on your electron-counting, what feature(s) about the W-NMe2 bonding/geometry might you
expect to show up in an X-Ray structure of this complex?
 Sabhuku Mudavanhu
Organometallic Exam # 2 (2007) 2

c) (5 pts BONUS) How would you explain the structure of W(NMe2)6 if it showed all approximately planar
W-NMe2 ligands (trigonal planar geometry about the nitrogen center)?

3. (15 pts) Consider the following reaction sequence:

CD3
H2C
Me 3P Br
 Ir C1

H H Br CD3 Br Br PMe3
C H2C
PMe3
Me3 P CD 3 Me3 P
Ir Ir +
Br PMe3 migr ator y Br PMe3 CH2D
inser tion D2C
PMe3 PMe3
Me 3P Br
A B Ir C2
Br PMe3
PMe3
The deuterated methyl group in the complex A does a migratory insertion with the carbene ligand to form the
ethyl group in B. Migratory insertion is the reaction of an anionic ligand with a neutral ligand to produce a new
anionic ligand (examples: M-carbene + M-CD3 M-CH2CD3; M-ethylene + M-H M-Et). The
product C2, however, shows that one can get some scrambling of the deuterium labels from the original CD3
methyl group. Clearly explain and show the properly labeled reaction steps that convert B to C2. Don’t worry
about bromide coordination till the last step. [Hint: an ethylene ligand can freely rotate about the metal-
ethylene bond]
 Sabhuku Mudavanhu
Organometallic Exam # 2 (2007) 3

4. (20 pts) Consider the following two substitution reactions. Sketch out the most likely reaction steps to
produce the most stable product (substitute only one ligand with that shown). Briefly & clearly state your
reasoning/explanation for each reaction and the final product shown.

O
C
(t-Bu-O) 3P
a) Fe C O + PMe3
(t-Bu-O)3P
P(O-t-Bu) 3

H3C SMe2
Ni + CO
b)
H3C O

5. (10 pts) Explain why square-planar d8 complexes of Rh(+1), Ir(+1), Ni(+2), Pd(+2), Pt(+2), and Au(+3) are
stable with 16e- configurations and why they only bind a fifth ligand weakly (to moderately).
 Sabhuku Mudavanhu
Organometallic Exam # 2 (2007) 4

6. (15 pts) Circle the complex that should have the weakest M-CO bonding. Clearly explain your answer.

a) Tc(CH3)(CO)5 -or- Re(F)(CO)5

b) WO3(CO)3 -or- Cr(CMe)(CO)4

c) HCo(CO)4 -or- HMn(CO)4(PMe3)

7. (10 pts) [CpIr(dmpe)(Et)]+ is quite stable while [CpCo[P(OMe)3]2(Et)]+ readily reacts with one equivalent
of PMe3 to produce {CpCo(H)(PMe3)[P(OMe)3]}+ plus a gas that bubbles off the solution.

a) (5 pts) Write out a mechanism for the reaction of [CpCo[P(OMe)3]2(Et)]+ to form

{CpCo(H)(PMe3)[P(OMe)3]}+.

Co CH3
(RO)3P C
H2
(RO)3 P

b) (5 pts) Why is [CpIr(dmpe)(Et)]+ considerably more stable?

 Sabhuku Mudavanhu
CHEM 4571 - Organometallic Chemistry Printed Name ______________________
EXAM # 2 - April 17, 2008 Signature__________________________
Check this box if you want your graded test put out
Please answer all questions! in the public boxes outside Prof. Stanley’s office:

1. (30 pts) For each of the following pairs of metal complexes, circle the one that will have the most labile
(easily substituted) carbonyl ligand. Briefly and clearly discuss your reasoning for each case including the
major factors influencing the correct answer.

a) WO2(NMe2)2(CO) -or- OsO2Me2(CO)2

b) Ni(CO)4 -or- W(CO)6

c) Pt(CO)2(PMe3)2 -or- NiF2(CO)2

d) [V(CO)6] -or- Fe(CO)4(PPh3)

e) Mn(Cl)(CO)5 -or- Mo(CO)6

f) CpWO2(CH3)(CO) -or- Cp2Ti(PMe3)(CO)

 Sabhuku Mudavanhu
Organometallic Exam # 2 (2008) 2

2. (30 pts) Identify the following reactions by their type (-hydride elimination, oxidative addition, reductive
elimination, associative substitution, dissociative substitution, ligand addition, ligand dissociation, ligand
coordination change, oxidative coupling, etc.). In some cases a reaction that may have several steps. In that
case list each step, and if the order of steps is important, list them in the correct order.
Me3P Me3P
Ni Ni
Me3P Me3P
a)

b) Re(SiMe3)(CO)5 + PMe3 Re(SiMe3)(CO)4(PMe3) + CO

c) CpRu(Et)(NCCH3)2 CpRu(H)(CH2=CH2)(NCCH3) + NCCH3

d) CpRh(PMe3)2 + C6H6 CpRh(H)(Ph)(PMe3) + PMe3

e) Cp2HfCl2 + CH3 Cp2HfCl(CH3) + Cl

f) PtCl(CH3)3(PMe3)(NCCF3) PtCl(CH3)(PMe3)(NCCF3) + CH3CH3

 Sabhuku Mudavanhu
Organometallic Exam # 2 (2008) 3

3. (30 pts) For each of the following pairs of metal complexes, circle the one that will most readily do an
oxidative addition with the reactant shown. No discussion is necessary.

a) H2: RhCl(CO)(PPh3)2 -or- RhI(CO)(PPh3)2

b) CH3Br: [Mn(CO)5] -or- [V(NR)2(CH3)2(PMe3)]

c) SiH4: Cp2Re(CH3) -or- (5-indenyl)RuCl(dppe)

d) Br2: [Cr(CH3)(NCMe)(dppe)2] -or- W(NMe2)6

f) H2: Fe(PMe3)2(CO)3 -or- MnCl(dppe)2

g) C6H5I: Pd(dmpe)(PMe3)2 -or- Cp2TaO(CH3)

4. (30 pts) Label the reaction steps marked with an empty box in the following catalytic cycle for the Pd-
catalyzed Heck coupling. Use the boxes provided and print clearly. A list of possible reaction steps is given
in problem 1.
 Sabhuku Mudavanhu
Organometallic Exam # 2 (2008) 4

5. (30 pts) Indicate the nature of the metal-ligand bonding for the specified ligand (charge may or may not be
indicated) in each of the following complexes by circling one of choices for the -bonding strength, -donor
ability, and -acceptor ability. Briefly and clearly explain each choice in the space provided.
a) NCH3 -bonding: weak medium strong
Reasoning:
in

Re(NCH3)(CH3)(CO)2(PPh3)

-donor ability: none weak medium strong

Reasoning:

-acceptor ability: none weak medium strong

Reasoning:

b) CF2 (neutral) -bonding: weak medium strong

Reasoning:
in

Cp*Ir(CF2)(CO)

-donor ability: none weak medium strong

Reasoning:

-acceptor ability: none weak medium strong

Reasoning:


Bonus (10 pts): Sketch out the just the Re(NCH3) portion of Re(NCH3)(CH3)(CO)2(PPh3) (from 5a) clearly
showing the Re-N bond order, the orientation of the methyl group on the NCH3 ligand, and location of any
non-bonding lone pair orbitals on the N atom (if present). No explanation needed.
 Sabhuku Mudavanhu

CHEM 4571 - Organometallic Chemistry Name __________________________

FINAL EXAM -- May 2007 Signature _______________________

Check this box if you want your graded test put out in the public boxes outside Prof. Stanley’s office:

1. (50 pts) Consider the cyclohydroamination reaction and catalysis cycle shown below:

2 + NH3 NH

7 1
H +
+ R3 P
+ PR 3 R3P
R3 P Ni Ni N R3P Ni Ni
R3 P R3P
N
H
+ NH3
6
H
R3P NH3
Ni
NH R3P Ni
HN
R3P

5  PR3

H H
R3P Ni R3 P
R 3P Ni R3 P Ni Ni
H2N H3N
4 H2N 3 H2 N
2
a) (40 pts) Label the indicated reaction steps below (no explanation required). There are two steps for 7,
the order of those may or may not be important.

(1)

(2)

(3)

(4)

(5)

(6)

(7a)

(7b)
 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 2

b) (10 pts) One of the reaction steps in the catalyst cycle generates a complex that is very unusual for Ni
but considerably more likely for Pd or Pt. Identify the complex (draw out the structure) and indicate
what is unusual about it and why it would be more likely with Pd or Pt.

2. (50 pts) The hydration of acetonitrile to produce organic amides is shown below.
O
H3C C N + H2O
H3C C NH2
a) (40 pts) Identify the one boxed mechanistic step in the catalytic cycle and draw in the three missing
boxed catalyst complexes for the steps shown. You may use Cp for cyclopentadienyl. Make sure you
keep proper track of the charge(s) on the complexes drawn!

2+
2  to  nitrile
+ CO3 coor dination
(depr otonation) change
N
Ir Ir
C H N H
Me O Me C
O
 HCO3
N H N
C
C CH 3
Me
O
+ H 2O
C
H 3C NH2 + nitrile

+ HCO3 pr oton
(protonation) transfer
Ir O
 CO32
N
C N Me
Me
H

b) (10 pts) Neutral catalysts do not work well for this reaction. Why?
 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 3

3. (50 pts) Hydroxycarbonylation (also referred to sometimes as hydrocarbonylation) is the catalyzed

reaction of alkenes, CO and water to make carboxylic acids:
O HO O
R + CO + H2O
R + *
HO R

side r eaction linear (normal) br anched (iso)

R Carboxylic Acids

alkene isomer ization

a) (25 pts) Sketch out a catalytic cycle for this using the Monsanto/BP catalyst [RhI2(CO)2] and
propylene (CH3CH=CH2) as your alkene to make the linear carboxylic acid product. HI is a co-
catalyst as in the Monsanto acetic acid process. The reactions steps in the proper order are as follows:
1) oxidative addition of HI, 2) CO ligand substitution of propylene (clearly indicate whether this is
an associative or dissociative ligand substitution rxn; this is also the rate-determining reaction step),
3) migratory insertion, 4) another migratory insertion and ligand addition, 5) reductive elimination of
acyl iodide and regeneration of starting [RhI2(CO)2] catalyst. In a separate step outside the Rh cycle
the acyl iodide reacts with water to produce the final product and regenerate what species that re-
enters the catalytic cycle?

OC CO
Rh
I I
HI
 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 4

b) (10 pts) This catalyst system has poor linear to branched carboxylic acid selectivity (about 1:1). What
would be the effect of replacing a carbonyl ligand with one P(i-Pr)3 ligand (i-Pr = iso-propyl)?
Consider the effect on both the rate of catalysis and selectivity to the linear carboxylic acid. Clearly
explain your reasoning.

c) (15 pts) It is known that HI can react directly with an alkene to produce an alkyl iodide:
I
+ HI I +

Sketch out and label the reaction steps showing how CH3CH2CH2I could react with the [RhI2(CO)2]
catalyst to produce the acyl iodide intermediate (not the entire cycle). Briefly discuss how (if) this
would affect the catalytic reaction.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 5

4. (50 pts) Sketch out a reasonable catalytic cycle for the following reaction and clearly label each step.
Make sure that the # of ligands on the catalyst and the electron-counting is OK. Indicate the electron-
count for each metal complex (but do NOT show the detailed electron-counting). Use the catalyst
precursor complex shown at the top of the catalytic cycle to generate your active catalyst by reaction
with HBR2 (R = non-bulky alkyl group) to eliminate CH4 (don’t forget to label what this step is
called).
hydroboration
BR2
+ HBR2

Sc CH3 catalyst precursor

 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 6

5. (50 pts) Bill Crowe’s research group (LSU Chem) has studied the following cyclocarbonylation rxn.

+ CO O
O O
a) (30 pts) Label the boxed reaction steps in my proposed catalytic cycle (there may be more than one
reaction occurring in each step, if the order is important label them 1), 2), etc.).

-CO O CO
CO CO H
Ti Ti Ti
CO
O

-CO

+2CO O
O
Ti

O
+CO

O
CO
Ti Ti
O
O

b) (15 pts) One might start with Cp2Ti(CH3)2 and react it with excess CO to produce the active
Cp2Ti(CO)2 catalyst and acetone (CH3(C=O)CH3). Clearly sketch out and label the reaction steps to
accomplish this. You don’t have to draw out the Cp rings on the complexes (use Cp).

c) (5 pts) This rxn is not really catalytic as the following reaction step is extremely slow and difficult.
Why? (briefly but clearly explain)
O
+2CO
+
CO
Ti Ti O
O CO
O
 Sabhuku Mudavanhu

CHEM 4571 - Organometallic Chemistry Name __________________________

FINAL EXAM -- May 2008 Signature _______________________

Check this box if you want your graded test put out in the public boxes outside Prof. Stanley’s office:

1. (50 pts) Bergman and coworkers reported the following transformation (JACS, 2002, 124, 4192-4193)
that was also presented in your notes:
* *
Rh + HSiPh3 Rh + CH 4
Me 3P N Me 3 P C
H3C C H 3C N
CH 3 SiPh 3

a) (35 pts) Shown below is a hypothetical catalytic cycle to transform acetonitrile (N≡CCH3) and HSiPh3
into the silyl-substituted isocyanide (C≡NSiPh3) and CH4. Label the forward steps (going clockwise)
in the catalytic cycle using the boxes provided. There may be more than step per box – if the order is
important label the steps 1) and 2), otherwise don’t number the steps.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 2

b) (5 pts) The last ligand substitution step in the cycle (perhaps the simplest step) is very unlikely to
occur and keeps this from being a real catalytic reaction. Clearly discuss why this step is unlikely to
happen.

c) (5 pts) What other step in the catalytic cycle is rather unusual and difficult? Clearly discuss.

d) (5 pts) In the following sequence of steps, the dissociation of the N-atom from the Rh center is very
important. Clearly discuss why this is important for the final reaction step.
* * *
Rh Rh N SiPh 3 Rh
Me 3 P Me 3P Me 3P C
C C
CH 3 N
N H 3C SiPh3
H3C
Ph 3Si
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 3

2. (50 pts) Hydroamination is the following catalytic process:

+ NHMe2 NMe2

Sketch out a reasonable catalytic cycle for hydroamination using RhCl(H2C=CH2)3 as the starting
catalyst. Clearly show and label each step in the cycle.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 4

3. (50 pts) Shown below is a proposed catalytic cycle for the hydrothiocarbonylation of an alkyne.
O
R + CO + HSR R
RS

a) (35 pts) Label each step in the catalytic cycle. There may be more than one thing occurring per step –
if the order is important, list them in the correct order.

H PPh3
Pt
R OC SR
R

H PPh3 PPh3
Pt Pt
OC SR OC SR

+ HSR O
R
RS
O PPh3
OC Pt PPh3 Pt
R
SR
+ CO

OC PPh3
Pt
O
SR

b) (10 pts) The alkyne addition step as written above is probably NOT correct due to a property of the Pt
center that makes this ligand addition unlikely. Discuss what I am referring to and a simple way to
correct this reaction step.

c) (5 pts) Assume that there is some excess PPh3 present, along with excess CO and alkyne. In the
bottom ligand addition step I used CO as the added ligand. Why is CO the best choice relative to
PPh3 or alkyne ligand?
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 5

4. (50 pts) One of the side reactions in the Monsanto acetic acid process is the water-gas shift reaction:
H2O + CO H2 + CO2
Using RhI3(CO)3 as the starting catalyst, sketch out a catalytic cycle for this based on the following
reaction steps: 1) nucleophillic attack of water on a carbonyl ligand followed by loss of a proton
(keep track of your charges on the complex!); 2) ligand dissociation (pick best ligand, keep track of
charges on your complex); 3) β-hydride elimination and loss (dissociation) of CO2; 4) ligand
addition (the one you dissociated); 5) protonation of hydride to dissociate H2 (proton from first
reaction step, keep track of charges on your complex); 6) ligand addition to regenerate starting
catalyst.

O
C
OC I
Rh
OC I
I
+ H2O
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 6

5. (50 pts) The two bisphosphine ligands shown in part a) are both excellent at generating very
regioselective (high linear to branched aldehyde ratios) Rh-based hydroformylation catalysts (alkene +
H2 + CO linear aldehyde). The proposed catalysis cycle is shown below with some side
complexes:

a) (20 pts) Which bisphosphine ligand shown to the

right generates a considerably more active Rh
hydroformylation catalyst and why? Only consider PPh 2
electronic effects, both ligands have similar steric O O
factors. O P P O
PPh 2
O O

UC-44 Naphos
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 7

b) (20 pts) Beller and coworkers have reported (Angew. Chem., 2001, 40, 3408-3411) on hydro-
formylation catalysis using HRh(CO)(Naphos). The table of catalytic data from their paper is shown
below. For experiment # 1, what is the theoretical maximum of turnovers that could have been done
and how many turnovers did the authors actually do?

c) (10 pts) Why is the hydroformylation of 2-pentene (cis and trans isomers are about the same) slower
than 1-pentene (Table 1 above, experiments #1 and #3)? Why is experiment # 4 especially slow?
Clearly explain and discuss.
 Sabhuku Mudavanhu

CHEM 4571 – Organometallic Chemistry ANSWER KEY

EXAM # 1 – Feb 15, 2007

Check this box if you want your graded test put out
Please answer all questions! in the public boxes outside Prof. Stanley’s office:

1. (60 pts) Sketch out the structure of the following transition metal complexes as accurately as possible
and clearly show the electron counting (including the oxidation state of the metal center and ligand
charges if present). You don’t have to draw out phenyl rings on ligands (e.g., for PPh3).

a) [Co(CH3)3Cl3]3−
Cl 3- Co(+3) d6
3CH3− 6e-
Cl CH3
Co 3Cl− 6e-
Total 18 e-
Cl CH3
CH3

b) CpW(NO)(CO)(PR3)
W(0) d6
Cp− 6e-
NO+    2e-
W PR3 2e-
R3P C
O CO 2e-
N Total 18 e-
O

c) [Rh2(μ-dppm)2(μ-Cl)(N≡CMe)2]+ (dppm = Ph2PCH2PPh2)

Me Rh(+1) d8
Me Ph2P PPh2
C C μ-Cl− 2e-
N N
2PR3 4e-
Rh Rh N≡CR 2e-
Cl Total 16 e-
Ph2P PPh2

d) Cp2Ta(CCH3)
Ta(+5) d0
2Cp− 12e-
≡CR3− 6e-
Ta CR Total 18 e-

e) Cp2Co
Co(+2) d7
2Cp− 12e-
Total 19 e-
Co
 Sabhuku Mudavanhu
Exam # 1 (2007) 2

f) [AuCl2Ph2]− (Ph = C6H5)

Cl Au(+3) d8
2Ph− 4e-
Au 2Cl− 4e-
Total 16 e-
Cl

g) V(NCH3)Cl3(dppe) (dppe = Ph2PCH2CH2PPh2)

R V(+5) d0
Ph2 N 3Cl− 6e-
P Cl dppe (2PR3) 4e-
V ≡NR2- 6e-
P Cl Total 16 e-
Ph2 Cl

h) Ir2(μ-OMe)2(H2C=CH2)4
R Ir(+1) d8
2μ-OR−
O
4e-
Ir Ir 2H2C=CH2 4e-
O Total 16 e-
R

i) Cp2Zr(NMe2)(η1-CH2CH=CH2)
Zr(+4) d0
2Cp− 12e-
NR2−
CH2
4e-
Zr
NR2 η1-allyl 2e-
Total 18 e-

j) [CpW(PR)(CO)3)]+
W(+4) d2
Cp− 6e-
PR2− 4e-
W
RP C 3CO 6e-
C O Total 18 e-
C
O
O

k) [Cr2(CH3)8]4−
H3C CH3 4- Cr(+2) d4
H3 C Cr CH3 4CH3− 8e-
4Cr-Cr 4e-
Total 16 e-
H3C Cr CH3
H3 C CH3

l) V(CO)6
O V(0) d5
C 6CO 12e-
O
C C
O Total 17 e-
V
C C
O C O
O
 Sabhuku Mudavanhu
Exam # 1 (2007) 3

2. (30 pts) For each of the following pairs of complexes, which will have the highest average CO infrared
stretching frequency? Circle your choice and briefly explain your reasoning.
The least electron-rich metal will π-backbond the least with the
a) Ni(CO)4 - or - [V(CO)6]− CO ligands and have the highest CO stretching frequency

V is very electropositive and in a very electron-rich -1 oxidation state, so it will π-backbond the most and have
the lower CO stretching frequency. Although Ni has more d electrons (d10), it is considerably more
electronegative and will have the higher CO stretching frequency.

b) CpNb(CR)Cl(CO) - or - CpV(CH3)2(CO)

The Nb complex is d0 and can not π-backbond, so it will automatically have the higher CO stretching frequency.
The V complex is d2 with good donor ligands and can π-backbond reasonably well.

c) Cr(CO)3(PMe3)3 - or - MnCl(CO)5

The Cr complex has 3 strong PMe3 σ-donors and only 3 CO ligands. So the Cr will be more electron-rich than
the Mn(+1) complex that has a poor chloride donor and 5 π-backbonding CO ligands. Mn is also more
electronegative than Cr.

d) Cp2Zr(CO)2 - or - [RhCl2(CO)2[P(OMe)3]2]+

The Rh complex has a cationic charge that will contract the metal d orbitals, poor σ-donors (phosphite and
chloride), and the phosphite ligands can also compete for the π-backbonding. This makes the Rh complex the
more electron-poor and the one with the higher CO stretching frequency. The Zr complex is d2 and in a rather
low oxidation state (likes to be +4 and d0). The Cp anions are strong donors and the CO ligands will be strongly
π-backbonding to the Zr center.

e) [Rh(CO)4]+ - or - [Ir(CH3)2(CO)2(PMe3)2]+

Both complexes are cationic, but the Ir has 4 strong donor groups and only 2 CO ligands. So it will be more
electron-rich and do more π-backbonding giving a lower CO stretching frequency.

f) Mo(dmpe)2(CO)2 - or - W(dmpe)(CO)4 (dmpe = Me2PCH2CH2PMe2)

The Mo complex has two strong donating dmpe ligands (alkylated phosphines) and only 2 CO ligands. So it will
be more electron-rich and the CO π-backbond more. The lower electronegativity of the W is a minor factor easily
overridden by the ligand effects.
 Sabhuku Mudavanhu
Exam # 1 (2007) 4

3. (20 pts) Consider the isocyanide (C≡NR, sometimes called isonitrile) and nitrile (N≡CR) ligands that are
isomers of one another.
a) (10 pts) Sketch out a Lewis dot diagram for each showing the location of the lone pair(s) and any formal
charges based on organic valence conventions.

N C CH3 C N CH3

b) (5 pts) Which ligand is the better σ-donor? Why?

C≡NR is the better σ-donor because the carbon atom has the lone pair of electrons and it less
electronegative than the N atom in the nitrile. This will make the lone pair have a higher energy (better
donor) and greater extent giving better overlap with the metal d orbital.

c) (5 pts) Which ligand is the better π-acceptor? Why?

C≡NR is the better π-acceptor because the empty π* orbital has

greater orbital extent on the carbon atom due to the carbon atoms C N CH3 N C CH3
lower electronegativity. This allows the isocyanide π*-orbital to have
better overlap and bonding with the filled metal d orbital.

4. (40 pts) Sketch out a neutral 18-electron structure showing the geometry about the metal center as
accurately as you can at this point in the course for the following metals and ligands. Use at least one
metal and each type of ligand shown. Try to keep your structure as simple as possible (bimetallic
complexes are OK, nothing higher). Clearly show your electron counting. Ligands are shown without
charges, please indicate the proper ligand charge and metal oxidation state in your electron counting.

a) Mo, μ-CR2, dmpe, CO b) Nb, NMe, NMe2, Cp, Cl

O O Mo(+2) d4 Nb(+5) d0
C C 2 μ-CR22− 4e- Cp− 6e-
NR2−
R2
C dppe (2PR3) 4e- 6e-
P Mo Mo P 2 CO 4e- Nb NR2− 4e-
P C P Mo=Mo 2e-
Cl N Cl− 2e-
C R2 C Total 18 e-
R Total 18 e-
R2N
O O

c) Ru, C6H6, H, PMe3 d) Mn, CH3, CO

Ru(+2) d6 CH3 Mn(+1) d6

C 6H 6 6e- O
C C
O CH3− 2e-
2H− 4e- Mn 5CO 10e-
PR3 2e- C C Total 18 e-
Ru O O
Total 18 e- C
H PR3
H O
 Sabhuku Mudavanhu

CHEM 4571 – Organometallic Chemistry ANSWER KEY

EXAM # 1 – Feb 21, 2008
Check the box to the right if you want your graded exam to be placed in the public rack outside
Prof. Stanley’s office. Otherwise you will have to pick it up from Prof. Stanley in person:

Please answer all questions!

1. (40 pts) Sketch out the structure of the following transition metal complexes as accurately as possible
and clearly show the electron counting for each including the metal oxidation state and ligand charges.
You don’t have to draw out phenyl rings on ligands (e.g., PPh3).

a) [Cr(PH2)(CO)5] −

Cr(0) 6e-
PH2 PH2− 2e-
OC CO 5 CO 10e-
Cr Total 18 e-
OC CO
CO
b) Cp2Rh2(μ-NHMe)2

H CH3 Rh(+2) 7e-

Cp− 6e-
N
2 μ-NHMe− 4e-
Rh Rh Rh-Rh 1e-
N Total 18 e-
H3C H

c) [ReCl(H2C=CH2)(dppe)2]+ [dppe = Ph2PCH2CH2PPh2]

Re(+2) 5e-
Ph2 Ph2 Cl− 2e-
P P C=C 2e-
Re 2 dppe 8e-
P P
Ph2 Ph2 Total 17 e-
Cl
d) CpY(NR2)(CH3)(THF) (THF = O )
Y(+3) 0e-
Cp− 6e-
NR2− 4e-
Y CH3− 2e-
R2N O THF 2e-
CH3 Total 14 e-

e) CpMo(PMe3)2(C≡CMe)(CO)
Mo(+2) 4e-
Cp− 6e-
CCR− 2e-
2 PR3 4e-
CO 2e-
Total 18 e-
 Sabhuku Mudavanhu
Exam # 1 (2008) 2

f) [trans-AuI2Ph2] − (Ph = C6H5)

Au(+3) 8e-
I 2 Ph− 4e-
trans means that the two Ph− and I− ligands
2 I− 4e- should be opposite one another
Ph Au Ph Total 16 e-

g) V(NMe)Cl3(CH3OCH2CH2OCH3)

V(+5) 0e-
NR2− 6e-
2 R-O-R 4e-
3 CI − 6e-
Total 16 e-

h) Ir2(μ-Br)2(CO)4

OC Br CO Ir(+1) 8e-
Ir Ir 2μ-Br− 4e-
2CO 4e-
OC Br CO Total 16 e-

2. (40 pts) For each of the following pairs of complexes, which will have the lowest average CO infrared
stretching frequency? Circle your choice and briefly explain your reasoning.
The most electron-rich metal with d-electrons will π-backbond the most
a) CpFe(CO)2(PF3) -or- CpOs(CO)(PMe3)2 with the CO ligands and have the lowest CO streaching frequency

The Os complex has two strongly donating PMe3 groups and only one π-backbonding CO, thus this one CO
ligand will π-backbond more strongly with the metal center. The Os is also less electronegative and will be willing
to π-backbond more strongly to the CO.

b) Cp2Y(CH3)(CO) -or- Cp2V(CH3)(CO)

The Y complex is a d 0 system and can not π-backbond to the CO. The V complex, on the other hand, is a d 2
complex and has strongly donating Cp− and CH3− groups

c) Cr(CO)4(PEt3)2 -or- W(CO)4(PPh3)2

The two PEt3 ligands on the Cr complex are strongly σ donating, considerably more so than the PPh3 ligands.
This more than compensates for the higher electronegativity of Cr vs. W.

d) PtCl4(CO)2 -or- NiBr2(CO)2

The Ni(+2) complex is more electron-rich than the Pt(+4) complex since it has a lower oxidation state (more d
electrons) and better donor ligands (Br − vs. Cl − ). The Pt is less electronegative and has 4 donor ligands vs. just
two for the Ni complex, so that tends to compensate and make them closer together. Since they could be
considered reasonably close to one another based on these two different lines of reasoning, we will give full credit
for either answer so long as the justification is OK.
 Sabhuku Mudavanhu
Exam # 1 (2008) 3

3. (30 points) a) (20 pts) Show the charges (may be 0) and number of electron pairs (may be zero) on the
donor atoms that will coordinate to the metal center for the following chelating ligands:

F atoms attached to C or As are too electronegative to act as ligands.

The As lone pairs are much higher in energy and better donors.

b) (10 pts) Order the ligands above from strongest to weakest donor for a Zr(+4) metal center and include
your reasoning. You can refer to the ligands by their primary donor atom type (e.g., S, O, N, etc) and do
not have to sketch them out.
O > N > S > As
Zr(+4) is a “hard” early transition metal center that is highly oxophillic (oxygen-loving), especially for
anionic “harder” ligands like O, N, C, or Cl. So the O (two anionic donors) > N (one anionic, one neutral
donor) ranking is fairly straightforward based on this. S and As are both “softer” ligands, but S is less
polarizable than As (fewer core electrons) so it should bind more strongly relative to As-based ligands.

4. (40 pts) Sketch out a neutral 18-electron structure showing the geometry about the metal center as
accurately as you can at this point in the course for the following metals and ligands. Use at least one
metal and each type of ligand shown. Try to keep your structure as simple as possible (bimetallic
complexes are OK, nothing higher). Show your electron counting. Ligands are shown without charges,
please indicate the proper ligand charge and metal oxidation state in your electron counting.

a) W, μ-PR2, CO, H b) Hf, Cp, N≡CCH3, NCH3

W(+2) 4e- Hf(+4) 0e-

2μ-PR2− 4e- NR2− 4e-
H− 2e- 2 Cp− 12e-
4CO 8e- NCMe 2e-
Total 18 e- Total 18 e-

c) Pt, CH, Cl, PMe3 d) Nb, O, CH3, Cp, PMe3

Pt(+4) 6e- Nb(+5) 0e-

CH3− 6e- Cp− 6e-
Cl− 2e- Nb O 2− 6e-
2PMe3 4e- Me3P O 2CH3− 4e-
Total 18 e- CH3 PMe3 2e-
H3C
Total 18 e-

Bonus (10 pts): Why is C≡NMe a weaker π-acceptor than C≡O? There are two primary reasons.

Nitrogen is less electronegative (electron-withdrawing) than oxygen and the methyl group on the nitrogen is
a sigma donor making the N more electron-rich and a poorer electron acceptor.
 Sabhuku Mudavanhu
CHEM 4571 - Organometallic Chemistry ANSWERS
EXAM # 2 - March 29, 2007
Check this box if you want your graded test put out
Please answer all questions! in the public boxes outside Prof. Stanley’s office:

1. (20 pts) Which of the following metal hydrides should be the most acidic? Clearly explain your reasoning.
The most electron-poor metal center will have the most
a) HNb(CO)6 -or- HV(CO)5(PMe3) acidic hydride ligand.

The V complex has a strong donor alkylated phosphine ligand, thus making it more electron-rich than the Nb
complex.

b) HRh(CO)(PPh3)2 -or- HRh(CO)2[P(OPh)3]

The circled complex has the most and best π-acceptor (electron-withdrawing) ligands (2 carbonyls & one
phosphite). This makes it more electron-deficient and most able to handle the negative charge and lower Rh
oxidation state after H+ loss.

c) [HOs(PMe3)(dmpe)2]+ -or- HRe(CF3)2(CO)2[P(OMe3)3]2

This was from homework # 2. The circled complex has the best π-acceptor (electron-withdrawing) ligands
(2 carbonyls & 2 phosphites) and worst donor ligands. This makes it more electron-deficient and most able
to handle the negative charge and lower Re oxidation state after H+ loss. The Os complex, despite it’s
positive charge, has all strongly donating alkylated phosphine ligands.

d) [HCoCl(NH3)4]+ -or- CpFe(H)(dppe)

The circled complex has a Co(+3) center, poor σ-donors (amines & chloride), and a positive charge. This
makes it more electron-deficient and most able to handle the negative charge and lower Co oxidation state
after H+ loss. The Fe complex has a good Cp− donor and a medium donor dppe bisphosphine.

2. (10 pts) a) (5 pts) Electron-count W(NMe2)6 clearly showing the W oxidation state, ligand charges, and #
of electrons donated from the ligands to the metal center.
NMe2 W(+6) d0 Use three amides that are 4e- donors and three
NMe2 3 M=NMe2− 12e- that are 2e- donors to get to 18e-. Using all six as
2e- donors only gives you a very unsaturated 12e-
Me2N W NMe2 3 M-NMe2− 6e-
count that is too low considering that the amide
Me2 N Total 18e- ligands can potentially donate 4e-.
NMe2

b) (5 pts) Based on your electron-counting, what feature(s) about the W-NMe2 bonding/geometry might you
expect to show up in an X-Ray structure of this complex?
You might expect to see the three double bonded W=NMe2 ligands
with shorter W-N bond distances, while the three with single bonds W N Me
W N
Me Me
should have longer bond distances. The geometry of the W-amide
will also change with the bonding: the double bonded amides will be Me
sp2 hybridized and have trigonal planar geometry, while the singly W =N R2 4 e- donor
2
W -NR 2 2e - d onor
sp hy brid ize d sp 3 hy br idized
bonded amides will have pyramidal geometry with an uncoordinated t rigona l planar about N py ra midal about N
lone pair of electrons.
 Sabhuku Mudavanhu
Organ
nometallic Exam
m # 2 (2007) 2

c) (55 pts BONU US) How wo ould you expplain the struucture of W((NMe2)6 if itt showed all approximately planar
W
W-NMe 2 lig
gands (trigon
nal planar geoometry abouut the nitrogeen center)?
There are se
T everal possib
ble explanations:
1 Delocalizzed bonding would resullt in an avera
1) age W-N bond order of 1.5, a bond length interm mediate
between a localized single and double
d bond, and a strucctural geome etry about thhe N of the amide
a ligand
that is in between trig
gonal planarr and pyramidal. This would
w look ap
pproximatelyy trigonal pla
anar.
2 N atoms occasionally
2) y prefer a trigonal planar sp2 hybridiized geomettry with the lone pair ressiding in a
pure p-tyype orbital. Only
O three of
o these would donate 4e e- to the mettal, while the
e other three
e amides
would acct as 2e- don nors. One might
m then exxpect to see different W--N bond distances unlesss
delocalizzed bonding is occurring (likely).
3. (15 pts) Conssider the folllowing reacttion sequence:
CD
D3
H2C
Me 3P Br
B
Ir C1
H H Br− CD3 Br − Br P 3
PMe
C H2C
PMe3
M 3P
Me CD 3 Me3 P
Ir Ir +
Br PMe3 migr ator y Br PMe3 CH
H2D
inser tion D2C
PMe3 PMe3
Me 3P B
Br
A B Ir C2
Br PMe
P 3
PMe3
The deuterated methyl
m groupp in the compplex A does a migratoryy insertion with
w the carbeene ligand too form the
ethyll group in B. Migratoryy insertion is the reactionn of an anionnic ligand wiith a neutral ligand to prooduce a neww
anionnic ligand (eexamples: M-carbene
M + M-CD
M 3 M-CH2CD C 3; M-ethyylene + M-H H M-Ett). The
prodduct C2, howwever, showss that one cann get some scrambling
s o the deuterrium labels from
of fr the origginal CD3
methhyl group. Clearly
C explaain and showw the properlly labeled reaction steps that convertt B to C2. Don’tD worry
abouut bromide coordination till the last step.
s [Hint: an ethylenee ligand can freely rotatee about the metal-
m
ethyllene bond]

CD3 Br− H D Br− D H Br − CH2D Br −

H2C C C D C C H D2 C
H D
Me
e3P Me
e3P D Me3P D Me3P
Ir Ir Ir Ir C2
B
Br PMe
e3 Br
B PMe
e3 Br P 3
PMe Br PMe3
PMe3 PMe3 PMe3 PMe
e3 brommide
β -hy drid e et hy lene migr atorry liga
and
elimination r ot ati on inser tionn addiit ion
B 16e- 18e- 18e- 16e-- 18e-

B is a 16e- comp plex that has s an empty orbital

o next to
t the ethyl (CH
( 2CD3) grroup. This allows
a a β-hyydride
elimiination to ma
ake the 18e-- ethylene-Irr-deuteride complex.
c Ro otation of the
e ethylene group to placce the CH2
portion in proxim
mity to the Ir--D bond then
n leads to a migratory insertion to make
m the 16e
e- Ir-CD2-CHH2D
complex, followe ed by bromid de ligand addition to the empty orbital to make C2.
C
 Sabhuku Mudavanhu
Organometallic Exam # 2 (2007) 3

4. (20 pts) Consider the following two substitution reactions. Sketch out the most likely reaction steps to
produce the most stable product (substitute only one ligand with that shown). Briefly & clearly state your
reasoning/explanation for each reaction and the final product shown.
O O O
C C C
− P(OR)3 + PMe3
(t-Bu-O) 3P (t-Bu-O) 3 P (t-Bu-O) 3P
a) Fe C O + PMe3 Fe C O Fe C O
(t-Bu-O)3P ligand (t-Bu-O)3P ligand (t-Bu-O)3P
dis sociat ion ad dit ion
P(O-t-Bu) 3 to open up PMe3
f ree coordinati on
18e- site 16e- 18e-
Since we are starting with an 18e- complex, we have to proceed by a dissociative substitution reaction. The phosphite
ligand is the more weakly coordinated and somewhat bulky due to the t-butyl groups. Thus it is the most likely ligand to
fall off first.
O
C
− THF
H3C SMe2 H3C SMe2 H3 C SMe2
b) Ni + CO Ni Ni
ligand ligand H 3C
H3C O addit ion
H3C O dissociation C
O

16e- 18e- 16e-

Since we are starting with an 16e- Ni complex without any steric problems we can to proceed by an associative
substitution reaction. Once the CO ligand coordinates, the weakest ligand that should fall off is the THF. Late transition
metals have a far stronger preference for S over O-based ligands.

5. (10 pts) Explain why square-planar d8 complexes of Rh(+1), Ir(+1), Ni(+2), Pd(+2), Pt(+2), and Au(+3) are
stable with 16e- configurations and why they only bind a fifth ligand weakly (to moderately).

Square-planar d8 complexes have an empty p-orbital (pz) perpendicular to the ligand plane (xy plane). This is
what incoming ligands would like to coordinate to. BUT, there is also a filled d-orbital (dz2) in the same exact
region of space. This filled orbital will repel the incoming ligand lone pair orbital. This results in a reasonably
stable 16e- configuration and generally weak coordination to a fifth ligand.

For Ni, Rh, and Pd the empty pz orbital is more spatially extended than the more contracted dz2 orbital and
favors weak bonding of the fifth ligand.

For Ir, Pt, and Au, the empty pz orbital is more contracted and the filled dz2 orbital more spatially expanded.
This leads to the filled orbital having a considerably stronger blocking effect on incoming ligands and a far
lower propensity for coordinating a fifth ligand.
 Sabhuku Mudavanhu
Organometallic Exam # 2 (2007) 4

6. (15 pts) Circle the complex that should have the weakest M-CO bonding. Clearly explain your answer.
The most electron-poor metal center will have the least
a) Tc(CH3)(CO)5 -or- Re(F)(CO)5 π-backbonding and the weakest M-CO bond.
The very poorly donating F− ligand will increase the amount of positive charge on the metal and reduce the
amount of π-backbonding to the carbonyls, weakening their bonding to the metal. This is a larger factor
than the third-row effect. The CH3− ligand in the Tc complex is strongly donating and will increase the
amount of π-backbonding to the Tc increasing the Tc-CO bond strength.

b) WO3(CO)3 -or- Cr(CMe)(CO)4

The W(+6) complex is d0, so there will be minimal π-backbonding to the carbonyls, thus giving the weakest
bonding to the metal. The Cr(+3) complex is d3 and has a very strongly donating trianionic 6e- donor
carbyne ligand.

c) HCo(CO)4 -or- HMn(CO)4(PMe3)

The Mn(+1) complex has a strong donor alkylated phosphine ligand, a d6 configuration, and the Mn is less
electronegative relative to Co. Thus, it should have more π-backbonding and stronger Mn-CO bonds.

7. (10 pts) [CpIr(dmpe)(Et)]+ is quite stable while [CpCo[P(OMe)3]2(Et)]+ readily reacts with one equivalent
of PMe3 to produce {CpCo(H)(PMe3)[P(OMe)3]}+ plus a gas that bubbles off the solution.

a) (5 pts) Write out a mechanism for the reaction of [CpCo[P(OMe)3]2(Et)]+ to form

{CpCo(H)(PMe3)[P(OMe)3]}+.

− P(OR) 3
Co CH3 Co CH3 Co CH 2
(RO) 3P (RO) 3P C (RO) 3P
C
H2
ligand
H2 β -hy drid e
(RO)3 P dissociation elimination H H 2C
t o open up
18e- f re e coor dinat ion 16e- 18e-
sit e The phosphite, P(OR)3, is
the weakest coordinating
− ethylene ligand and can fall off the
ligand easiest promoting the β-
+ PMe3 dis sociat ion
to open up
hydride elimination rxn.
Co Co f ree coordinati on
(RO)3 P ligand (RO)3 P site
PMe3 addit ion
H H
18e- 16e-

b) (5 pts) Why is [CpIr(dmpe)(Et)]+ considerably more stable?

The strong chelating dmpe (Me2PCH2CH2PMe2) ligand will not easily dissociate to open up an empty orbital
to allow β-hydride elimination to occur. The considerably more weakly coordinating phosphine ligand in (a)
can far more easily dissociate allowing the β-hydride elimination to occur.
 Sabhuku Mudavanhu
CHEM 4571 - Organometallic Chemistry ANSWER KEY
EXAM # 2 - April 17, 2008
Check this box if you want your graded test put out
Please answer all questions! in the public boxes outside Prof. Stanley’s office:

1. (30 pts) For each of the following pairs of metal complexes, circle the one that will have the most labile
(easily substituted) carbonyl ligand. Briefly and clearly discuss your reasoning for each case including the
major factors influencing the correct answer.
You are looking for the most electron-poor (or d 0 ) complex
a) WO2(NMe2)2(CO) -or- OsO2Me2(CO)2 that will have the smallest amount of π-backbonding to the CO

The W(+6) center is d0 and won’t be π-backbonding with the CO ligand allowing it to dissociate very easily.
The Os(+6) d2 complex (18e-), on the other hand can π-backbond and has some pretty good donor groups.

b) Ni(CO)4 -or- W(CO)6

Athough the Ni(0) center is d10 (vs. the W(0) d6 center) and has fewer CO ligands, the Ni complex has the
weaker CO π-backbonding due to the considerably higher electronegativity of the Ni center.

c) Pt(CO)2(PMe3)2 -or- NiF2(CO)2

The Ni(+2) center is d8, more electronegative than Pt, and has very poor donating F− ligands. This will
make the Ni center more cationic and engage in less π-backbonding with the CO ligands.

d) [V(CO)6]− -or- Fe(CO)4(PPh3)

The V(-1) d6 complex is in a very low oxidation state and will π-backbond extremely strongly with the CO
ligands and not want to dissociate them. The Fe(0) d8 center has one moderate donating ligand and is
more electronegative than the V center. The Fe-CO bond will dissociate the easiest.

e) Mn(Cl)(CO)5 -or- Mo(CO)6

The Mn(+1) center is d6, more electronegative than Mo (also d6), and has a poor donating Cl− ligand. This
will make the Mn center more cationic and engage in less π-backbonding with the CO ligands. The second
row Mo should also have somewhat stronger bonding to the CO’s vs. the first row Mn.

f) CpWO2(CH3)(CO) -or- Cp2Ti(PMe3)(CO)

The W(+6) center is d0 and won’t be π-backbonding with the CO ligand allowing it to dissociate very easily.
The Ti(+2) d2 complex (18e-), on the other hand is very electron-rich and will π-backbond extremely strongly
with the CO.
 Sabhuku Mudavanhu
Organometallic Exam # 2 (2008) 2

2. (30 pts) Identify the following reactions by their type (β-hydride elimination, oxidative addition, reductive
elimination, associative substitution, dissociative substitution, ligand addition, ligand dissociation, ligand
coordination change, oxidative coupling, etc.). In some cases a reaction that may have several steps. In that
case list each step, and if the order of steps is important, list them in the correct order.
Me3P Me3P
Ni Ni
Me3P Me3P
a)
oxidative coupling

b) Re(SiMe3)(CO)5 + PMe3 Re(SiMe3)(CO)4(PMe3) + CO

Dissociative substitution of CO with PMe3
-or-
1) CO ligand dissociation (18e- saturated complex, anionic SiMe3 ligand harder to dissociate)
2) PMe3 ligand addition

c) CpRu(Et)(N≡CCH3)2 CpRu(H)(CH2=CH2)(N≡CCH3) + N≡CCH3

1) N≡CCH3 ligand dissociation (to make 16e- complex with open orbital)
2) β-hydride elimination (to generate hydride and coordinated ethylene)

d) CpRh(PMe3)2 + C6H6 CpRh(H)(Ph)(PMe3) + PMe3

1) ligand dissociation (PMe3)

2) oxidative addition of benzene C-H bond

e) Cp2HfCl2 + CH3− Cp2HfCl(CH3) + Cl−

Associative substitution (16 e- Hf complex without any steric problems)

-or-
1) CH3− ligand addition (to make an 18e- anionic complex)
2) Cl− ligand dissociation

f) PtCl(CH3)3(PMe3)(N≡CCF3) PtCl(CH3)(PMe3)(N≡CCF3) + CH3CH3

1) N≡CCH3 ligand dissociation (to make 16e- complex which is more electron-deficient)
2) reductive elimination of two CH3− groups to make ethane
3) ligand addition of N≡CCH3
-or-
Direct reductive elimination of two CH3− groups to make ethane (less likely, but possible)
 Sabhuku Mudavanhu
You are looking for d 2 or higher systems that are the most electron-rich. For non-
Organometallic Exam # 2 (2008) electrophillic substrates like H2 or SiH4 you also need an empty orbital or a ligand that 3
will dissociate most readily to make an empty orbital.
3. (30 pts) For each of the following pairs of metal complexes, circle the one that will most readily do an
oxidative addition with the reactant shown. No discussion is necessary.

a) H2: RhCl(CO)(PPh3)2 -or- RhI(CO)(PPh3)2 Iodide is a stronger donor than chloride

b) CH3Br: [Mn(CO)5]− -or- [V(NR)2(CH3)2(PMe3)]− V(+5) = d0

c) SiH4: Cp2Re(CH3) -or- (η5-indenyl)RuCl(dppe) Indenyl can easily shift to η3 to give 16e- count

d) Br2: [Cr(CH3)(N≡CMe)(dppe)2]+ -or- W(NMe2)6 W(+6) = d0

f) H2: Fe(PMe3)2(CO)3 -or- MnCl(dppe)2 Mn = 16e- d6, has empty orbital

g) C6H5I: Pd(dmpe)(PMe3)2 -or- Cp2TaO(CH3) Ta(+5) = d0

4. (30 pts) Label the reaction steps marked with an empty box in the following catalytic cycle for the Pd-
catalyzed Heck coupling. Use the boxes provided and print clearly. A list of possible reaction steps is given
in problem 1.
ligand
addition Ph3P
Pd PPh3
Br
PPh3
oxidative
HBr addition
reductive + PPh3
elimination
Br PPh3 Ph3P PPh3
Pd Pd
Ph3P H Ph3P + Br

- PPh3
dissociative
+ Br substitution

Br PPh3
Br PPh3 Pd
Pd Ph3P
Ph3P H

-hydride ligand
elimination addition

Br PPh3 Br PPh3
Pd Pd
Ph3P Ph3P
migratory
insertion
 Sabhuku Mudavanhu
Organometallic Exam # 2 (2008) 4

5. (30 pts) Indicate the nature of the metal-ligand bonding for the specified ligand (charge may or may not be
indicated) in each of the following complexes by circling one of choices for the σ-bonding strength, π-donor
ability, and π-acceptor ability. Briefly and clearly explain each choice in the space provided.
a) NCH3 σ-bonding: weak medium strong
Reasoning:
in The dianionic [N-CH3]2− ligand is a strong σ-donor due to the negative 2 charge
and donating methyl group.
Re(NCH3)(CH3)(CO)2(PPh3)

[N-CH3]2− is an imido π-donor ability: none weak medium strong

ligand: 4 or 6e- donor Reasoning:
The negative 2 charge and presence of three filled lone pairs makes this a
powerful π-donating ligand that can make 1 or 2 π-bonds to the metal (4 or 6e-
donor)

π-acceptor ability: none weak medium strong

Reasoning:
There are NO empty low lying π* or other empty orbitals to act as π-acceptors of
d-electrons from the metal center.

b) CF2 (neutral) σ-bonding: weak medium strong

Reasoning:
in The electron-withdrawing F atoms, neutral charge, and unfilled-octet (only 6
valence electrons) makes it a poor σ-donor.
Cp*Ir(CF2)(CO)

π-donor ability: none weak medium strong

CF2 (neutral) is a Reasoning:
Fischer carbene with
The lack of any filled p-orbital or extra lone pairs means that it cannot act as a π-
electron-withdrawing
donor.
F atoms that makes it
a poor σ-donor but a
strong π-acceptor.
π-acceptor ability: none weak medium strong
Reasoning:
The electron-withdrawing F atoms, neutral charge, and low-lying empty p-orbital
makes it an excellent π-acceptor (almost as good as CO). The F atoms cannot
π-donate to the empty π-orbital on the carbon atom like O, N, S, or other π-donor
substituents.

Bonus (10 pts): Sketch out the just the Re(NCH3) portion of Re(NCH3)(CH3)(CO)2(PPh3) (from 5a) clearly
showing the Re-N bond order, the orientation of the methyl group on the NCH3 ligand, and location of any
non-bonding lone pair orbitals on the N atom (if present). No explanation needed.

[N-CH3]2− will act as a 6e- donor to get the Re(+3) d4 center up to an 18e- count.
The π-backbonding CO ligands will like maximum donation from the imido ligand
to make the Re center as electron-rich as possible.
 Sabhuku Mudavanhu

CHEM 4571 - Organometallic Chemistry ANSWER KEY

FINAL EXAM -- May 2007

Check this box if you want your graded test put out in the public boxes outside Prof. Stanley’s office:

1. (50 pts) Consider the cyclohydroamination reaction and catalysis cycle shown below:

2 + NH3 NH

Ni(2+), 14e- 7 H + 1 Ni(2+), 16e-

R3P
+ + PR3 R3 P
R 3P Ni Ni N R3 P Ni Ni
R3P R 3P
N
H Ni(0), 16e-
Ni(0), 18e- + NH3
6
H
R3P NH3
Ni(2+), 16e-
Ni
NH R3P Ni
HN
R3P
Ni(2+), 18e-

5 − PR3
Ni(2+), 16e-
H
R 3P H
Ni R3 P
R 3P Ni R3P Ni Ni
H 2N H 3N
H2N
4 H2N
3 2 Ni(2+), 16e-
Ni(0), 16e- Ni(4+), 16e-

a) (40 pts) Label the indicated reaction steps below (no explanation required). There are two steps for 7,
the order of those may or may not be important.

(1) oxidative coupling [two alkynes, Ni(0) to Ni(2+)]

(2) oxidative addition [N-H bond, Ni(2+) to Ni(4+)]

(3) reductive elimination [NH2− and CH=R−, Ni(4+) to Ni(2+)]

(4) reductive elimination [H− and CH=R−, Ni(2+) to Ni(0)]

(5) oxidative addition [N-H bond, Ni(0) to Ni(2+)]

(6) migratory insertion [H− and alkene to form alkyl]

(7a) reductive elimination [NH− + CH2R−, Ni(2+) to Ni(0), product coordinated due to N lone pair]

(7b) alkyne ligand addition

 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 2

b) (10 pts) One of the reaction steps in the catalyst cycle generates a complex that is very unusual for Ni
but considerably more likely for Pd or Pt. Identify the complex (draw out the structure) and indicate
what is unusual about it and why it would be more likely with Pd or Pt.

H 4+ is a very high and unusual oxidation state for Ni, which rarely goes above 2+.
This is due to the higher electronegativity of Ni relative to Pd and Pt, both of
R3P Ni which can readily form the 4+ oxidation state (d6 octahedral complexes)
because of their lower electronegativities.
H2N
Ni(4+), 16e- Everyone got credit for this question
(unless you didn’t write anything down).

2. (50 pts) The hydration of acetonitrile to produce organic amides is shown below.
O
H3C C N + H2O
H3C C NH2
a) (40 pts) Identify the one boxed mechanistic step in the catalytic cycle and draw in the three missing
boxed catalyst complexes for the steps shown. You may use Cp for cyclopentadienyl. Make sure you
keep proper track of the charge(s) on the complexes drawn!

2+
2− σ to π nitrile
+ CO3 coor dination
Ir (depr otonation) Ir change
N H N H N Ir
Me C O Me
C
O C H
Me O
− HCO3−
N H N N
C
C C CH 3 Ir(3+), 18e-
Ir(3+), 18e- Ir(3+), 18e-
Me Me
O
+ H 2O
migratory
H 3C
C
NH2 + nitrile insertion

2+

+ HCO3− pr oton
Ir O OH
(protonati on) transfer Ir
N Ir
C N Me O N N
Me − CO32− N C
H Me Me
H C N Me
Me
Ir(3+), 18e- H Ir(3+), 18e- Ir(3+), 16 or 18e-

b) (10 pts) Neutral catalysts do not work well for this reaction. Why?

The cationic charge is important to enable the hydrolysis (deprotonation) of coordinated water to form
the more reactive hydroxide ligand that can do the migratory insertion with the nitrile. Neutral metal
complexes won’t drain enough electron density from the weakly coordinated water ligand to allow
deprotonation by a weak to moderate base like carbonate. Strong bases generally won’t work here
because they will not release the H+ needed towards the end of the catalysis cycle.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 3

3. (50 pts) Hydroxycarbonylation (also referred to sometimes as hydrocarbonylation) is the catalyzed

reaction of alkenes, CO and water to make carboxylic acids:
O HO O
R +
R + CO + H2 O HO * R

side r eaction linear (normal) br anched (iso)

R Carboxylic Acids

alkene isomer ization

a) (25 pts) Sketch out a catalytic cycle for this using the Monsanto/BP catalyst [RhI2(CO)2]− and
propylene (CH3CH=CH2) as your alkene to make the linear carboxylic acid product. HI is a co-
catalyst as in the Monsanto acetic acid process. The reactions steps in the proper order are as follows:
1) oxidative addition of HI, 2) CO ligand substitution of propylene (clearly indicate whether this is
an associative or dissociative ligand substitution rxn; this is also the rate-determining reaction step),
3) migratory insertion, 4) another migratory insertion and ligand addition, 5) reductive elimination of
acyl iodide and regeneration of starting [RhI2(CO)2]− catalyst. In a separate step outside the Rh cycle
the acyl iodide reacts with water to produce the final product and regenerate what species that re-
enters the catalytic cycle?

O
OC CO
+ HI Rh
OH I I
HI
+ H2O
H
O
OC CO
Rh
I I I
I

- CO
+

O
H
+ 2CO
OC CO OC OC
Rh Rh Rh
I I I I I I
I I I

When water reacts with the acyl iodide it regenerates HI, the co-catalyst for the reaction.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 4

b) (10 pts) This catalyst system has poor linear to branched carboxylic acid selectivity (about 1:1). What
would be the effect of replacing a carbonyl ligand with one P(i-Pr)3 ligand (i-Pr = iso-propyl)?
Consider the effect on both the rate of catalysis and selectivity to the linear carboxylic acid. Clearly
explain your reasoning. Everyone got credit for this question (unless you didn’t write anything down).

Rate effect: Replacing one of the CO ligands with a strong donating

H alkylated phosphine will make the Rh even more electron-rich. This will
R3P CO increase substantially the π-backbonding with the last remaining CO ligand
Rh and make it’s dissociation far slower. This should dramatically slow down
I I the coordination of the alkene and slow the rate of catalysis. The one
I compensating factor could be that the more electron-rich metal will now be
more likely to dissociate an iodide ligand. The trans-effect will specifically
favor dissociating the iodide trans to the phosphine and coordination of the alkene at this site, which
is cisoidal to the hydride to perform the migratory insertion rxn.
Selectivity: The bulkier phosphine should generally favor the hydride-alkene migratory insertion to
produce the less hindered linear alkyl product, which will then go on to form the linear acyl-iodide and
carboxylic acid. Note, however, that the magnitude of the selectivity effect may well depend on
exactly where the phosphine is coordinated and how the alkene is oriented to the Rh-H bond and the
phosphine directing effect. For example, if the iodide ligand trans to the phosphine dissociated, the
trans phosphine would have essentially no steric effect on the coordinating alkene for the migratory
insertion step.

c) (15 pts) It is known that HI can react directly with an alkene to produce an alkyl iodide:
I
+ HI I +

Sketch out and label the reaction steps showing how CH3CH2CH2I could react with the [RhI2(CO)2]−
catalyst to produce the acyl iodide intermediate (not the entire cycle). Briefly discuss how (if) this
would affect the catalytic reaction.

1) migratory
insertion O
I
+ CO OC CO
OC CO OC CO
Rh Rh Rh
I I oxidative I I 2) ligand I I
addition I addition I

O
reductive
We only graded the mechanism part of this question. elimination
R I

This could actually speed up the rate of catalysis as the oxidative addition step is not dependent on
an empty coordination site opening up on the catalyst as is necessary for the alkene coordination and
subsequent reaction.
Extra: The bad aspect overall is the preferred formation of the branched alkyl iodide (2-iodo-
propane) that would react to make the branched carboxylic acid, a generally non-desirable product.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 5

4. (50 pts) Sketch out a reasonable catalytic cycle for the following reaction and clearly label each
step. Make sure that the # of ligands on the catalyst and the electron-counting is OK. Indicate the
electron-count for each metal complex (but do NOT show the detailed electron-counting). Use the
catalyst precursor complex shown at the top of the catalytic cycle to generate your active catalyst by
reaction with HBR2 (R = non-bulky alkyl group) to eliminate CH4 (don’t forget to label what this step
is called).
hydroboration
BR2
+ HBR2

Sc CH3 14e-
Maximum points taken off = 25
(unless you didn’t write anything down) cataly st precursor

+ HBR2
Hy dr ogenoly sis
- CH 4

BR2

ligand addition
Sc BR2

Hy dr ogenolysis 14e-

BR2

Sc BR 2
Sc
H
R2B

16e- (B-H sigma bond) 16e-

+ HBR 2 BR2

ligand addition Sc
migratory inser tion

14e-
 Sabhuku Mudavanhu
Organometallics Final Exam – 2007 6

5. (50 pts) Bill Crowe’s research group (LSU Chem) has studied the following cyclocarbonylation rxn.

+ CO O
O O
a) (30 pts) Label the boxed reaction steps in my proposed catalytic cycle (there may be more than one
reaction occurring in each step, if the order is important label them 1), 2), etc.).

-CO O CO
CO CO H
Ti Ti Ti
CO
O

ox idativ e add ition

-CO
ligand dissociation
CO ad d ition
ligand add ition
r ed uctiv e +2CO O
elimination O
Ti
CO ad d ition
O
+CO

O
CO
1) mi gr ator y insert ion
Ti Ti
O
O 2) CO ligand add ition

migrator y
insert ion

b) (15 pts) One might start with Cp2Ti(CH3)2 and react it with excess CO to produce the active
Cp2Ti(CO)2 catalyst and acetone (CH3(C=O)CH3). Clearly sketch out and label the reaction steps to
accomplish this. You don’t have to draw out the Cp rings on the complexes (use Cp).

CO
Ti
1) reductive CO
O elimination
CH3 C
CH3 +CO CH3 +CO
Ti Ti CO Ti Ti CH3
CH3 CH3 CH3
CH3 C C
+CO +
ligand migratory ligand
addition insertion addition 2) ligand
O O addition O
C
H3C CH 3

c) (5 pts) This rxn is not really catalytic as the following reaction step is extremely slow and difficult.
Why? (briefly but clearly explain)
The reductive elimination to take Ti(4+), d0, to
O Ti(2+), d2 is difficult due to the low electronegativity
+2CO
Ti Ti
CO
+ O of early transition metals and their preference for
O CO
O high oxidation states. This specific rxn will be
especially difficult because of the extremely strong
Ti-OR bond, more so than that shown above in part
Full credit, unless you didn’t b) involving weaker Ti-alkyl,acyl bonds.
write anything down.
 Sabhuku Mudavanhu

CHEM 4571 - Organometallic Chemistry ANSWER KEY

FINAL EXAM -- May 2008

Check this box if you want your graded test put out in the public boxes outside Prof. Stanley’s office:

1. (50 pts) Bergman and coworkers reported the following transformation (JACS, 2002, 124, 4192-4193)
that was also presented in your notes:
* *
Rh + HSiPh3 Rh + CH 4
Me 3P N Me 3 P C
H3C C H 3C N
CH 3 SiPh 3

a) (35 pts) Shown below is a hypothetical catalytic cycle to transform acetonitrile (N≡CCH3) and HSiPh3
into the silyl-substituted isocyanide (C≡NSiPh3) and CH4. Label the forward steps (going clockwise)
in the catalytic cycle using the boxes provided. There may be more than step per box – if the order is
important label the steps 1) and 2), otherwise don’t number the steps.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 2

b) (5 pts) The last ligand substitution step in the cycle (perhaps the simplest step) is very unlikely to
occur and keeps this from being a real catalytic reaction. Clearly discuss why this step is unlikely to
happen.
Isocyanides are more strongly bonding ligands relative to nitrile ligands like acetonitrile. They are not
only stronger σ-donors, but also stronger π-acceptors. Both of these work in concert to make them
relatively strongly bonding ligands. Thus, it will be difficult to replace a more strongly bonding ligand
like isocyanide with a weaker bonding ligand like acetonitrile. If acetonitrile was the solvent, the large
concentration present might drive the reaction for a while, but as more and more isocyanide is
produced it would bind to the catalyst and inhibit it by tying up the empty coordination sites.

c) (5 pts) What other step in the catalytic cycle is rather unusual and difficult? Clearly discuss.
The elimination of the methyl group from the complex shown below is unusual and difficult. As
discussed in your notes eliminating an alkyl group from a C-C bond is not easy due to the directed
nature of the C-C sp3 hybrid orbitals and the presence of C-H bonds that can short circuit the reaction
via β-hydride elimination. Here, however, the β-hydride elimination would generate a relatively high
energy ketene-imine and the CH3 elimination turns out to be more favorable.
* *
Rh N SiPh 3 Rh
Me 3P Me 3P C
C
H 3C N
H3C SiPh3

d) (5 pts) In the following sequence of steps, the dissociation of the N-atom from the Rh center is very
important. Clearly discuss why this is important for the final reaction step.
* * *
Rh Rh N SiPh 3 Rh
Me 3 P Me 3P Me 3P C
C C
CH 3 N
N H 3C SiPh3
H3C
Ph 3Si

In order to do the methyl group elimination, you need to have an empty orbital on the Rh center and
the first complex is 18e- saturated. The neutral nitrogen atom is the weakest donor and is the most
likely to dissociate and allow the vinyl-like group to rotate the methyl group over to interact with the
empty orbital on the Rh to enable the elimination reaction.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 3

2. (50 pts) Hydroamination is the following catalytic process:

+ NHMe2 NMe2

Sketch out a reasonable catalytic cycle for hydroamination using RhCl(H2C=CH2)3 as the starting
catalyst. Clearly show and label each step in the cycle.

There are some variants in the order of the steps, exact # of ligands (16e- or 18e- Rh(III) complex
shown at bottom) and the use of solvent or one of the other ligands present (ethylene, amine) to fill in
coordination unsaturation generated by the migratory insertion step. The migratory insertion of the
amide with the alkene is also OK (although hydride and alkene is somewhat more favorable).
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 4

3. (50 pts) Shown below is a proposed catalytic cycle for the hydrothiocarbonylation of an alkyne.
O
R + CO + HSR R
RS

a) (35 pts) Label each step in the catalytic cycle. There may be more than one thing occurring per step –
if the order is important, list them in the correct order.

alkyne R
ligand addition migratory insertion
H PPh3 (alkyne & SR )
Pt
R OC SR
R

H PPh3 PPh3
Pt Pt
OC SR OC SR

migratory insertion
oxidative + HSR O (CO & vinyl )
addition
R
RS
O PPh3
OC Pt PPh3 Pt
R
SR
+ CO

OC PPh3
reductive Pt CO ligand addition
elimination O
SR

b) (10 pts) The alkyne addition step as written above is probably NOT correct due to a property of the Pt
center that makes this ligand addition unlikely. Discuss what I am referring to and a simple way to
correct this reaction step.

Pt(+2) d8 16e- square planar complexes do NOT like to add a fifth ligand due to the blocking effect of
the extended 5dz2 filled orbital. It is better to propose the loss of the PPh3 ligand to make a 3-
coordinate 14e- complex first, then bind the alkyne ligand. The dissociated PPh3 ligand can then be
re-coordinated after the migratory insertion of the CO and vinyl group.

c) (5 pts) Assume that there is some excess PPh3 present, along with excess CO and alkyne. In the
bottom ligand addition step I used CO as the added ligand. Why is CO the best choice relative to
PPh3 or alkyne ligand?

CO is electron-withdrawing and will favor the following reductive elimination step. Remember that
reductive elimination is favored by π-accepting ligands or electron-deficient metal centers. You do
generate a rather unsaturated 14e- complex, but that isn’t too bad for a Pt(0) d10 center that is right
next to Au. Remember that Au(+1) d10 complexes strongly favor 14e- two-coordinate complexes.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 5

4. (50 pts) One of the side reactions in the Monsanto acetic acid process is the water-gas shift reaction:
H2O + CO H2 + CO2
Using RhI3(CO)3 as the starting catalyst, sketch out a catalytic cycle for this based on the following
reaction steps: 1) nucleophillic attack of water on a carbonyl ligand followed by loss of a proton
(keep track of your charges on the complex!); 2) ligand dissociation (pick best ligand, keep track of
charges on your complex); 3) β-hydride elimination and loss (dissociation) of CO2; 4) ligand
addition (the one you dissociated); 5) protonation of hydride to dissociate H2 (proton from first
reaction step, keep track of charges on your complex); 6) ligand addition to regenerate starting
catalyst.
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 6

5. (50 pts) The two bisphosphine ligands shown in part a) are both excellent at generating very
regioselective (high linear to branched aldehyde ratios) Rh-based hydroformylation catalysts (alkene +
H2 + CO linear aldehyde). The proposed catalysis cycle is shown below with some side
complexes:

Stronger donating
phosphines favor the
stronger binding of the π-
accepting CO ligand(s).
That makes these 5-
coodinate 18e-
complexes too stable and
unwilling to dissociate the
CO ligand to allow alkene
or H2 coordination.

a) (20 pts) Which bisphosphine ligand shown to the

right generates a considerably more active Rh
hydroformylation catalyst and why? Only consider PPh 2
electronic effects, both ligands have similar steric O O
factors. O P P O
PPh 2
O O

The bisphosphite ligand UC-44 will make the most

active Rh hydroformylation catalyst since it is the UC-44 Naphos

poorest donor and a better π-acceptor relative to

Naphos. The less electron-rich the metal center, the weaker the Rh-CO π-backbonding and the easier
it is to get the alkene and H2 ligands in to start and finish the hydroformylation catalytic cycle.
Phosphite ligands make some of the most active Rh hydroformylation catalysts known, although they
usually give poor regioselectivity due to their small size. UC-44 is sterically bulked up to compensate
for this. One major problem with phosphite ligands (UC-44 included) is that they fragment via a
number of pathways considerably more easily than ligands like PPh3 or Naphos (which also have their
own fragmentation problems).
 Sabhuku Mudavanhu
Organometallics Final Exam – 2008 7

b) (20 pts) Beller and coworkers have reported (Angew. Chem., 2001, 40, 3408-3411) on hydro-
formylation catalysis using HRh(CO)(Naphos). The table of catalytic data from their paper is shown
below. For experiment # 1, what is the theoretical maximum of turnovers that could have been done
and how many turnovers did the authors actually do?

Excess Naphos is not

relevant to the TON
calculation, but is
needed to make sure
all the Rh is complexed
with Naphos to
generate active catalyst

a) Theoretical Turnover # = 10,000 (0.01 mol % of catalyst)

b) Actual turnover # for experiment # 1:
There are two ways to calculate the TON:
(1.0 equivalent alkene/0.0001 equivalent of Rh)*(0.76 yield) = 7,600 TO
or: (475 hr -1)(16 hr) = 7,600 TO (average TOF multiplied by time of run)

c) (10 pts) Why is the hydroformylation of 2-pentene (cis and trans isomers are about the same) slower
than 1-pentene (Table 1 above, experiments #1 and #3)? Why is experiment # 4 especially slow?
Clearly explain and discuss.
2-pentene is a more sterically hindered alkene and has a harder time fitting into the empty binding site
on the HRh(CO)(bisphosphine) catalyst. 1-alkenes are the least sterically hindered and typically
hydroformylate the fastest.
Experiment # 4 is especially slow because the CO pressure has been increased to 50 bar. CO is a
considerably better ligand than 2-pentene (no steric hindrance) and the more that is present in
solution, the less 2-pentene that can coordinate to the Rh and be hydroformylated. Note that the
smaller 1-pentene can compete more effectively with the CO and the average TOF actually increases
for experiment # 2 relative to # 1.