THE

ORGANOMETALLIC
CHEMISTRY OF THE
TRANSITION METALS
THE
ORGANOMETALLIC
CHEMISTRY OF THE
TRANSITION METALS
Seventh Edition

ROBERT H. CRABTREE
Yale University, New Haven, Connecticut
This edition first published 2019
© 2019 John Wiley & Sons Inc.
Edition History
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Library of Congress Cataloging-in-Publication Data
Names: Crabtree, Robert H., 1948- author.
Title: The organometallic chemistry of the transition metals / Robert H.
Crabtree (Yale University, New Haven, Connecticut).
Description: Seventh edition. | Hoboken, NJ : Wiley, 2019. | Includes
bibliographical references and index.
Identifiers: LCCN 2019003168| ISBN 9781119465881 (hardback) | ISBN
9781119465867 (epub)
Subjects: LCSH: Organometallic chemistry. | Organometallic
chemistry–Problems, exercises, etc. | Organotransition metal compounds. |
Transition metals.
Classification: LCC QD411.8.T73 C73 2019 | DDC 547/.056–dc23 LC record available at
https://lccn.loc.gov/2019003168
Cover Design: Wiley
Cover Image: Courtesy of Robert H. Crabtree
Set in 11/12.5pt TimesTenLTStd by SPi Global, Chennai, India
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
CONTENTS

Preface xi
Acknowledgments xiii
List of Abbreviations xv

1 Introduction 1
1.1 Why Study Organometallic Chemistry?, 1
1.2 Coordination Chemistry, 3
1.3 Werner Complexes, 3
1.4 The Trans Effect, 7
1.5 Soft Versus Hard Ligands, 9
1.6 The Crystal Field, 10
1.7 The Ligand Field, 17
1.8 Two-Electron Three-Center Bonding, 19
1.9 Four-Electron Three-Center Bonding, 20
1.10 Back Bonding, 22
1.11 Trends in d Orbital Energies, 26
1.12 Types of Ligand, 27
References, 32
Problems, 33

2 Making Sense of Organometallics 35

2.1 The 18-Electron Rule, 35
2.2 Limitations of the 18-Electron Rule, 43
2.3 Electron Counting in Reactions, 45

v
vi CONTENTS

2.4 The Oxidation State Concept and its Limitations, 46

2.5 Electroneutrality, 52
2.6 Coordination Number and Geometry, 53
2.7 Effects of Complexation, 56
2.8 Differences between Metals, 58
References, 62
Problems, 63

3 Alkyls and Hydrides 65

3.1 Alkyls and Aryls, 65
3.2 Other σ-Bonded Ligands, 79
3.3 Metal Hydrides, 80
3.4 Sigma Complexes, 83
3.5 Bond Strengths, 86
References, 88
Problems, 89

4 Ligand Substitution 91
4.1 Metal Carbonyls, 91
4.2 Phosphines, 100
4.3 N-Heterocyclic Carbenes, 103
4.4 Dissociative Substitution, 105
4.5 Associative Substitution, 109
4.6 Redox Effects and Interchange Substitution, 111
4.7 Photochemical Substitution, 113
4.8 Counterions and Solvents in Substitution, 115
References, 116
Problems, 118

5 Pi Complexes 121
5.1 Alkene and Alkyne Complexes, 121
5.2 Allyl Complexes, 126
5.3 Diene Complexes, 130
5.4 Cyclopentadienyl Complexes, 133
5.5 Arenes and Other Alicyclic Ligands, 140
5.6 Metalacycles, 143
5.7 Stability of Polyene and Polyenyl Complexes, 144
References, 145
Problems, 145

6 Oxidative Addition and Reductive Elimination 147

6.1 Introduction, 147
6.2 Concerted Additions, 149
CONTENTS vii

6.3 SN 2 Pathways, 152

6.4 Radical Mechanisms, 153
6.5 Ionic Mechanisms, 155
6.6 Reductive Elimination, 156
6.7 Sigma Bond Metathesis, 162
6.8 Ligand-Assisted 1,2-Additions and Eliminations, 163
6.9 Oxidative Coupling, 164
6.10 Proton-Coupled Electron Transfer, 165
References, 166
Problems, 167

7 Insertion and Elimination 169

7.1 Introduction, 169
7.2 1,1-Insertion, 171
7.3 1,2-Insertion, 175
7.4 Outer Sphere Insertions, 179
7.5 α-,β-,γ-, and δ-Elimination, 180
References, 182
Problems, 182

8 Addition and Abstraction 185

8.1 Introduction, 185
8.2 Nucleophilic Addition to CO, 187
8.3 Nucleophilic Addition to Polyenes and Polyenyls, 189
8.4 Nucleophilic Abstraction, 196
8.5 Electrophilic Addition and Abstraction, 197
8.6 Single-Electron Transfer and Radical Reactions, 200
References, 201
Problems, 202

9 Homogeneous Catalysis 205

9.1 Catalytic Cycles, 205
9.2 Alkene Isomerization, 211
9.3 Hydrogenation, 213
9.4 Alkene Hydroformylation, 221
9.5 Alkene Hydrocyanation, 223
9.6 Alkene Hydrosilylation, 224
9.7 Coupling Reactions, 225
9.8 Organometallic Oxidation Catalysis, 227
9.9 Electrocatalysis, 229
9.10 Photoredox Catalysis, 229
9.11 Surface, Supported, Single-Atom and Cooperative Catalysis, 231
References, 233
Problems, 235
viii CONTENTS

10 Physical Methods 239

10.1 Mechanism, 239
10.2 1 H NMR Spectroscopy, 240
10.3 13 C NMR Spectroscopy, 243
10.4 31 P NMR Spectroscopy, 244
10.5 Dynamic NMR, 246
10.6 Spin Saturation Transfer, 249
10.7 T1 and the Nuclear Overhauser Effect, 250
10.8 IR Spectroscopy, 254
10.9 Crystallography, 256
10.10 Electrochemistry and EPR, 257
10.11 Computation, 259
10.12 Other Methods, 260
References, 262
Problems, 263

11 M–L Multiple Bonds 265

11.1 Carbenes, 265
11.2 Schrock Carbenes, 272
11.3 Carbynes, 276
11.4 Bridging Carbenes and Carbynes, 278
11.5 N-Heterocyclic Carbenes, 279
11.6 Multiple Bonds to Heteroatoms, 282
References, 285
Problems, 286

12 Metathesis, Polymerization, and Bond Activation 289

12.1 Alkene Metathesis, 289
12.2 Alkene Dimerization, Oligomerization, and Polymerization, 295
12.3 Activation of CO and CO2 , 301
12.4 C−H Activation, 305
12.5 Dehydrogenative Oxidation and Hydrogen Borrowing, 309
References, 311
Problems, 313

13 Green Energy and Materials Applications 317

13.1 Green Chemistry, 317
13.2 Energy Chemistry, 320
13.3 Clusters and Nanoparticles, 323
13.4 Organometallic Materials, 325
References, 332
Problems, 334
CONTENTS ix

14 Organic Applications 337

14.1 Carbon–Carbon and Carbon–Heteroatom Coupling, 338
14.2 Metathesis, 343
14.3 Cyclopropanation and C–H Insertion, 345
14.4 Hydrogenation, 346
14.5 Carbonylation, 348
14.6 Oxidation, 350
14.7 C–H Activation, 352
14.8 Click Chemistry and Cycloaddition, 355
14.9 Photoredox Catalysis, 356
References, 359
Problems, 360

15 Paramagnetic and High-Oxidation-State Complexes 363

15.1 Magnetism and Spin States, 364
15.2 Cyclopentadienyl Complexes, 371
15.3 f-Block Complexes, 373
References, 380
Problems, 381

16 Bioorganometallic Chemistry 383

16.1 Introduction, 384
16.2 Coenzyme B12 , 388
16.3 Nitrogen Fixation, 394
16.4 Nickel Enzymes, 402
16.5 Artificial Enzymes, 407
16.6 Biomedical and Biocatalytic Applications, 407
References, 410
Problems, 412
Appendix A: Useful Texts on Allied Topics 415
Appendix B: Major Reaction Types 419
Solutions to Problems 421

Index 437
PREFACE

This book is a study of the logic of organometallic chemistry, emphasized in Chapters

1–11, as well as some of its leading applications, emphasized in Chapters 12–16. It
should give starting scholars the passport they need to set out on this field, analyze
the literature, and develop their own approaches and ideas.

ROBERT H. CRABTREE
New Haven, Connecticut
May 2019

xi
ACKNOWLEDGMENTS

I again thank the many colleagues and readers who kindly helped in some way: Odile
Eisenstein, Gary Brudvig, Jim Mayer, Daniel Kim, Jaeyeon Hwang, Michael Jewess,
Jeremy Weber, Zican Shen, Hannah Lant, Tom van Westen, and R.K. Sharma. I also
thank the Department of Energy, Basic Energy Sciences for funding our work in
this area.
Textbooks were apparently highly valued by Dr. Johnson, the very distinguished
eighteenth century literary critic, as reported by his biographer and friend, James
Boswell:

I [Boswell] ventured to interrogate him [Dr. Johnson], “But, Sir, is it not somewhat
singular that you should happen to have Cocker’s Arithmetick about you on you[r] jour-
ney? What made you buy such a book at Inverness?”—He gave me a very sufficient
answer. “Why, Sir, if you are to have one book with you upon a journey, let it be a book
of science. When you have read through a book of entertainment, you know it, and it
can do no more for you; but a book of science is inexhaustible.”
Journal of a Tour in the Hebrides with Samuel Johnson LL.D.
by James Boswell, London, 1785, p. 152.

xiii
LIST OF ABBREVIATIONS

[] Encloses complex molecules or ions

◽ Vacant site or labile ligand
∘ Degrees Celsius
1∘ , 2 ∘ , 3 ∘ Primary, secondary, tertiary.
A Associative substitution (Section 4.4)
acac Acetylacetonate
AIBN Azobisisobutyronitrile (radical initiator)
AO Atomic orbital
Ar Aryl (e.g. C6 H5 )
at. Pressure in atmospheres
bipy 2,2′ -Bipyridyl
Bu Butyl
cata Catalyst
Chap. Chapter
CIDNP Chemically induced dynamic nuclear polarization (Section 6.3)
CN Coordination number
cod 1,5-Cyclooctadiene
coe Cyclooctene
cot Cyclooctatetraene
Cp, Cp* C5 H5 , C5 Me5
Cy Cyclohexyl
𝜕+ Partial positive charge
𝛿 Chemical shift (NMR)
Δ Crystal field splitting (Section 1.4)
ΔEN Electronegativity difference
ΔG‡ ΔH‡ ΔS‡ Free energy, enthalpy and entropy of activation needed to reach
the transition state for a reaction.
D Dissociative substitution mechanism (Section 4.3)
D–C Dewar–Chatt model of M(C= =C) bonding involving weak back
donation (Section 5.1)
d 𝜎 , d𝜋 𝜎-Acceptor and 𝜋-donor metal orbitals (see Section 1.4)
diars Me2 AsCH2 CH2 AsMe2
dpe or dppe Ph2 PCH2 CH2 PPh2
dmf Dimethylformamide

xv
xvi LIST OF ABBREVIATIONS

dmg Dimethyl glyoximate

dmpe Me2 PCH2 CH2 PMe2
DMSO Dimethyl sulfoxide
dn Electron configuration (Section 1.4)
𝜂 Hapticity in ligands with contiguous donor atoms (e.g. C2 H4 .
See Section 2.1)
E, E+ Generalized electrophile such as H+
e Electron, as in 18e rule
e.e. Enantiomeric excess (Section 9.2)
en H2 NCH2 CH2 NH2
eq Equivalent or equatorial
Et Ethyl
EPR Electron paramagnetic resonance
Eq. Equation
eu Entropy units
eV Electron volt (1 eV = 23 kcal/mol)
EXAFS X-ray absorption edge fine structure spectroscopy
Fig. Figure
Fp (C5 H5 )(CO)2 Fe
fac Facial (stereochemistry)
GC gas chromatography
Hal Halogen
HBpz3 Tris(pyrazolyl)borate
HMPA Hexamethyl phosphoramide O= =P(NMe2 )3
HOMO Highest occupied molecular orbital
hs High spin
I Nuclear spin
I Intermediate substitution mechanism
IPR Isotopic perturbation of resonance (Section 10.8)
IR Infrared
𝜅 Hapticity in ligands with noncontiguous donor atoms (e.g.
H2 NCH2 CH2 NH2 . See Section 2.1)
L Depending on the context, L can be a generalized ligand of any
type, or else a 2e ligand in connection with the L model for
ligand binding discussed in Section 2.1)
Ln M Metal fragment with n generalized ligands
lin Linear
lp lone pair
ls low spin
LUMO Lowest unoccupied molecular orbital
μ Descriptor for bridging with a superscript for the number of
metals bridged, as in M3 (μ3 -CO)
m- Meta
MCP Metalacyclopropane model of M(C= =C) bonding involving strong
back donation (Section 5.1)
LIST OF ABBREVIATIONS xvii

Me Methyl
mer Meridional (stereochemistry)
mr Reduced mass
MO Molecular orbital
𝜈 Frequency
N Group number of M (=number of valence e in the neutral atom).
nbd Norbornadiene
NHC N-heterocyclic carbene (Section 4.2)
NHE Normal hydrogen electrode, a common standard potential
NMR Nuclear magnetic resonance (Sections 10.2–10.8)
NOE Nuclear Overhauser effect (Section 10.7)
Np Neopentyl
Nu, Nu− Generalized nucleophile, such as H−
o- Ortho
OA Oxidative addition
OAc Acetate
oct Octahedral (Table 2.6)
OS Oxidation state (Section 2.4)
oz. Ounce (28.35g)
p- Para
PE Polyethylene
PP Polypropylene
Ph Phenyl
pin Pinacolate
PNP A pincer ligand with one nitrogen and two phosphorus donors
py Pyridine
R Alkyl
RE Reductive elimination
RF Radiofrequency
RF Fluoroalkyl (e.g. CF3 )
Sec. Section of the book
SET Single electron transfer (Section 8.6)
𝜎-CAM 𝜎-Complex assisted metathesis
solv Solvent
sq. pl. Square planar
sq. py. Square pyramidal (Table 2.6)
T A structure with three of the ligands disposed as in the letter T.
T1 Spin–lattice relaxation time
tacn 1,4,7-Triazacyclononane
tacn* N,N′ ,N′′ -trimethyl-1,4,7-triazacyclononane
tbe t-BuCH= =CH2
tet Tetrahedral
thf Tetrahydrofuran ligand (but THF when a solvent)
triphos MeC(CH2 PPh2 )3
TBP or trig. bipy Trigonal bipyramidal (Table 2.6)
xviii LIST OF ABBREVIATIONS

TMEDA Me2 NCH2 CH2 NMe2

TMS Tetramethylsilyl or tetramethylsilane
Tp Tris(pyrazolyl)borate (5.37)
Ts p-TolylSO2
TTP Tricapped trigonal prism (Table 2.6)
VB Valence bond
X Generalized 1e anionic ligand (Section 2.1)
Y A structure with three of the ligands disposed as in the letter Y.
GROUP
1 Periodic Table of the Elements 18
1 2
H He
1.0079 2 13 14 15 16 17 4.0026
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.0122 10.811 12.011 14.007 15.999 18.998 20.180
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.990 24.305 3 4 5 6 7 8 9 10 11 12 26.982 28.086 30.974 32.066 35.453 39.948

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 Ga Ge As Se Br Kr
39.088 40.078 44.956 47.867 50.942 51.996 54.938 55.845 58.933 58.693 63.546 65.39 69.723 72.61 74.922 78.96 79.904 83.80
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
85.468 87.62 88.906 91.224 92.906 95.94 98.906 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29
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 .
132.91 137.33 138.91 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 209.98 209.99 222.02
87 88 89 104 105 106 107 108 109 110 111 112
Fr Ra . Ac Rf Db Sg Bh Hs Mt
223.02 226.03 227.03 (261) (262) (266) (262) (269) (266) (273) (272) (294)

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanide
series Ce Pr Nd Pm. Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.12 140.91 144.24 146.92 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

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

Actinide
series Th . Pa . U Np . Pu . Am. Cm. Bk . Cf . Es . Fm. Md. No . Lr .
232.04 231.04 238.03 237.05 239.05 241.06 244.06 1249.08 252.08 252.08 257.10 258.10 259.10 262.11
Note: et al., Inorg. Chim. Acta 1994, 217, 217).
An astcrisk indicates the mass of a commonly known radioisotope. Numbers in parentheses are the mass numbers of the corresponding longer-lived isotope.

xix
1
INTRODUCTION

Organometallic chemistry fills in a gap and makes a conceptual link between organic
and inorganic chemistry in its focus on the binding of organic fragments to metals via
one or more M–C bonds. The metals can come from the main group, in the s and p
blocks of the periodic table, as in the Grignard reagent, CH3 MgBr, or from the tran-
sition elements of the d and f blocks, as in the ethylene complex salt, K[(C2 H4 )PtCl3 ].
Main-group organometallics, such as n-BuLi and PhB(OH)2 , have proved so useful
for organic synthesis that they are extensively covered in organic chemistry courses
and textbooks. Here, we look instead at the transition metals where the intervention
of metal d and f orbitals opens reaction pathways not otherwise accessible. While
main-group organometallic reagents are typically stoichiometric – used in a simple
mole ratio with the reactant – many transition metal organometallics are now most
often seen as catalysts, where the metal-to-reactant ratio is typically 1 : 100 but can
be 1 : 106 or even beyond. The higher the ratio, the greater the practicality of an
organometallic catalyst, even if expensive.

1.1 WHY STUDY ORGANOMETALLIC CHEMISTRY?

The expanding range of applications of transition metal catalysis in organic chemistry

helped explain the rise of d block organometallics from the late twentieth century.
As late as 1975, the great majority of organic syntheses had no recourse to transition
metals at any stage; in contrast, they now almost always appear, often as catalysts.
Catalysis is also a central principle of the twenty-first century field of green or sus-
tainable chemistry1 because it helps avoid the waste formation in chemical processes,
for example, of Mg salts from Grignard reactions, and its high selectivity minimizes
the need for product separations.

The Organometallic Chemistry of the Transition Metals, Seventh Edition. Robert H. Crabtree.
© 2019 John Wiley & Sons, Inc. Published 2019 by John Wiley & Sons, Inc.
1
2 INTRODUCTION

In 2012, the noted organic chemist and Associate Editor of the Journal of Organic
Chemistry, Carsten Bolm2 , published a ringing endorsement of organometallic meth-
ods as applied to organic synthesis:

In 1989, OMCOS-VI [the 6th International Conference on Organometallic Chemistry

Directed Toward Organic Synthesis] took place in Florence and … left me with the
impression that all important transformations could – now or in the future – be per-
formed with the aid of adequately fine-tuned metal catalysts. Today, it is safe to say that
those early findings were key discoveries for a conceptual revolution that occurred in
organic chemistry in recent years. Metal catalysts can be found everywhere, and many
synthetic advances are directly linked to … developments in catalytic chemistry.

Organometallics have a much longer history in industrial chemistry. In the 1880s,

Ludwig Mond refined crude nickel in a stream of hot CO to volatilize the Ni as
Ni(CO)4 ; subsequent stronger heating then deposited pure Ni. From the 1930s,
the Co2 (CO)8 catalyzed hydroformylation of 1- or 2-butene with H2 and CO was
applied to n-pentanal and n-pentanol manufacture. From the 1970s right up to
today, a variety of homochiral pharmaceuticals have been produced by asymmetric
catalysis, in which racemic reagents are transformed into single pure product
enantiomers. Other examples include alkene polymerization to give polyethylene
and polypropylene, hydrocyanation of butadiene for nylon manufacture, acetic
acid synthesis from MeOH and CO, and hydrosilylation to produce silicone
materials.
We are beginning to see applications elsewhere. From 2001, Cu catalyzed “click”
chemistry has allowed coupling molecular units even within living cells or in
advanced materials3 . Some of the organic light-emitting diodes (OLEDs) in cell
phone displays rely on organometallics. Samsung has produced OLED screens
since 2008 that use a cyclometallated Ir complex as the red emitter. They are
also useful in solid-state light-emitting electrochemical cells (LECs)4 . Photoredox
catalysis (Section 14.9) is a rising field in organic synthesis in which a favored
photosensitizer is an organometallic iridium complex resembling the OLED
emitters.
Surprisingly, organometallics have a multibillion year history in biology. Although
most metalloenzymes employ classical coordination chemistry, the metal ions being
surrounded by N- or O-donor ligands, a small but growing class of organometallic
metalloenzymes is emerging. Ligands such as CO and CN− appear in hydrogenases
and even a carbide in nitrogenase, both being enzymes that are believed to have
evolved very early in the Earth’s history. Biomedical applications are beginning to
be seen: organometallic pharmaceuticals5 such as the antimalarial, ferroquine, and
the antitumoral, ferrocifen, are also emerging, together with a variety of diagnostic
imaging agents such as cardiolite6 .
Another practical problem7 , alternative energy research, is driven by climate
change concerns8 . Solar and wind energy being intermittent, the resulting electrical
energy needs to be converted into a storable fuel. This is most plausibly done by
splitting water into O2 and either H2 or 2(H+ + e− ) that can reduce CO2 to a fuel
such as MeOH. This strategy, termed artificial photosynthesis, needs catalysts some
of which are organometallic9, 10 .
WERNER COMPLEXES 3

1.2 COORDINATION CHEMISTRY

Along with M–C bonds, organometallic compounds often also contain N- or O-donor
coligands typical of coordination chemistry. Mixed ligand sets being so common,
the distinction between coordination and organometallic chemistry is increasingly
blurred. More importantly, organometallics are governed by many of the principles
of coordination chemistry, so we look at these next11 .
The fundamentals of metal–ligand bonding were first established for coordina-
tion compounds by the founder of the field, Alfred Werner (1866–1919) who was
even able to identify the octahedral geometry of CoL6 complexes without the aid of
modern spectroscopy or crystallography12 .
Central to our modern understanding both of transition metal coordination and
organometallic compounds are d orbitals. Main-group compounds either have a filled
d level that is too stable (e.g. Sn) or an empty d level that is too unstable (e.g. C)
to participate significantly in bonding. Partial filling of the d orbitals in the d block
metals gives them their characteristic properties. Some early transition metal ions
with no d electrons (e.g. group 4 Ti4+ ) and some late metals with a filled and stable set
of 10e (e.g. group 12 Zn2+ ) more closely resemble main-group elements. The terms
“early” and “late” here refer to the left-hand (e.g. Ti, V, Ta, etc.) versus the right-hand
side (e.g. Cu, Pd, Ir, etc.) d block elements.
Transition metal ions can bind ligands (L) to give a coordination compound, or
complex MLn , as in the familiar aqua ions [M(OH2 )6 ]2+ (M = V, Cr, Mn, Fe, Co,
or Ni). Organometallic chemistry can thus also be seen as a subfield of coordina-
tion chemistry in which the complex contains an M–C bond. Even in the absence
of M–C bonds, compounds with M–Q bonds where the atom Q has an electronega-
tivity similar to C (e.g. M–SiR3 , M–H, etc.) also have organometallic properties and
are treated here. Organometallic M–L bonds tend to be more covalent than M–N
or M–O bonds of coordination compounds because the electronegativity difference
between M and C is lower than for M and N or O. Typical C-donor ligands that usu-
ally bind to metal ions in their more reduced, low-valent forms are CO, alkenes, and
arenes, as in zerovalent Mo(CO)6 , Pt(C2 H4 )3 , and (C6 H6 )Cr(CO)3 . Higher valent
states are beginning to play a more important role, however, particularly with alkyl
and aryl ligands, as in hexavalent WMe6 and pentavalent O= =Ir(mesityl)3 (Chap. 15).

1.3 WERNER COMPLEXES

Werner complexes consist of a central metal, M, surrounded by ligands, L, that con-

tain electronegative donor atoms, typically O, N, or halide. The ligand lone pairs
bind to the metal to form such complexes as [Co(NH3 )6 ]3+ , the M–L bond having
a marked polar covalent character. The M–NH3 bond itself consists of the 2e of the
lone pair of free NH3 but now shared with the metal in a polar covalency.

Stereochemistry
The most common type of complex, octahedral ML6 , adopts a geometry (1.1) based
on the Pythagorean octahedron. By occupying its six vertices, the ligands can form
4 INTRODUCTION

M–L bonds, while maximizing the L … L nonbonding distances. The solid and dashed
wedges in structure 1.1 indicate bonds that point toward or away from us, respec-
tively.

Octahedron

The complex may have a net ionic charge to make a complex ion (e.g. [PtCl4 ]2− );
together with the counterions, we then have a complex salt (e.g. K2 [PtCl4 ]). In some
cases, both cation and anion may be complex, as in the picturesquely named Mag-
nus’ green salt [Pt(NH3 )4 ][PtCl4 ], where the square brackets enclose the individual
ions.
Ligands with more than one lone pair can donate each pair to different metals to
form bridges in polynuclear complexes, such as 1.2 (L = PR3 ). The bridging group
is represented by the Greek letter μ (mu) as in [Ru2 (μ-Cl)3 (PR3 )6 ]+ . Dinuclear 1.2
consists of two octahedra sharing a face containing three chloride bridges.

Chelate Effect
Ligands with more than one donor atom, such as ethylenediamine (NH2 CH2 CH2
NH2 , or “en”), can donate both lone pairs to a single metal to form a chelate ring
(1.3). The most favorable ring size is five, but six is also common. Chelating ligands
are much less easily displaced from a complex than are comparable monodentate lig-
ands. For example, the reactants in Eq. (1.1) release six NH3 molecules, increasing the
total number of particles from four to seven; this creates entropy and so favors the
chelate. Each chelate ring usually stabilizes the complex by about 105 in the equi-
librium constant for the reaction. Such equilibrium constants are called formation
constants; the higher the value, the more stable the complex.

[M(NH3)6]n+ + 3en → [M(en)3]n+ + 6NH3 (1.1)

WERNER COMPLEXES 5

Chelate ligands can also be polydentate, as in tridentate 1.4 and hexadentate 1.5.
As a tridentate planar ligand, 1.4 is termed a pincer13, 14 . Ethylenediaminetetraacetic
acid (EDTA, 1.5) can take up all six sites of an octahedron and thus completely wrap
up most metal ions. Reactivity in metal complexes usually requires open sites or at
least labile sites at the metal. The food preservative EDTA acts by binding free metal
ions, blocking all the sites so that they can no longer catalyze aerial oxidation of the
foodstuff.

Werner’s Coordination Theory

Alfred Werner developed the modern picture of coordination complexes in the years
following 1893, when, as a young scientist, he proposed that the cobalt ammines
(ammonia complexes) have an octahedral structure as in 1.6, where the abbreviated
square brackets stand in for the full set in structures 1.2 and 1.3.
+ +

In doing so, he rejected the then-standard view that the ligands were bound in chains
with the metal at one end (e.g. 1.7). The third chloride ion was thought to be weakly
attached to the chain and so easily dissociating in water. Naturally, Werner was
opposed by supporters of the standard model who were only willing to slightly adjust
their model to take account of his new data. Jørgensen, who led the traditionalists
against the Werner insurgency, would not accept that a trivalent metal, Co3+ , could
form more than the three bonds needed in the chain theory. At first, as each new
“proof” came from Werner, Jørgensen was able to point to problems in the proof or
reinterpret the chain theory to fit the new facts. For example, coordination theory
calls for two isomers of [Co(NH3 )4 Cl2 ]+ (1.6 and 1.8). Up to then, only a green one
was known, Werner’s trans isomer (1.6), so called because the two Cl ligands occupy
opposite vertices of the octahedron. According to Werner, a second isomer, 1.8 (cis),
having adjacent Cl ligands should exist. Not only was it then unknown but initial
attempts to make it failed. Changing the chloride to nitrite, Werner was indeed
able to obtain both green cis and purple trans isomers of [Co(NH3 )4 (NO2 )2 ]+ (1.9
and 1.10). Jørgensen quite reasonably – but wrongly – countered this by saying
that the nitrite ligands in the two isomers were simply bound differently (linkage
6 INTRODUCTION

isomers), via N (Co–NO2 ) or O (Co–ONO) (1.11 and 1.12). Undismayed, Werner

then produced the green and purple isomers, 1.13 and 1.14, of [Co(en)2 Cl2 ]+ , in a
case where no linkage isomerism was possible. Somewhat less plausibly, Jørgensen
brushed this observation aside by invoking different chain arrangements as in 1.15
and 1.16.
+ +

In 1907, Werner finally made the elusive purple isomer of [Co(NH3 )4 Cl2 ]+ by an
ingenious route (Eq. (1.2)) via the necessarily cis carbonate [Co(NH3 )4 (O2 CO)].
Treatment with HCl in the solid state at 0 ∘ C liberated CO2 and gave the elusive
cis dichloride. Jørgensen, receiving a sample of this purple complex by mail, finally
conceded defeat.

+ +
(1.2)
THE TRANS EFFECT 7

On resolving optical isomers of the halides [Co(en)2 X2 ]+ (1.17 and 1.18), Werner
argued that the isomerism could only arise from the octahedral array, not otherwise.
Even this point was challenged by traditionalists on the grounds that only organic
compounds could be optically active, and so this activity must come from the organic
ligands in some undefined way. Werner responded by resolving a complex (1.19) con-
taining only inorganic elements. This has the extraordinarily high specific rotation of
3.6 × 104 ∘ and required 1000 recrystallizations to resolve.

Cl + Cl +
H2 H2
N Cl Cl N
Co Co
N NH2 H2N N
H2 H2
H2N NH2
1.17 1.18

NH3 6+
H3N NH3
Co
NH3 HO NH3
H3N OH OH
Co Co
H3N OH OH
NH3 HO NH3
Co
1.19 H3N NH3
NH3

Several important conclusions follow. Scientific ideas are only provisional, so some
of our current ones are likely to be wrong – we just do not know which ones. The
literature must thus be read critically with an eye for possible flaws in the results,
inferences, or arguments. Nugent has reviewed a series of ideas, once generally held,
that subsequently fell from grace15 . Another cogent lesson from Werner is that we
must take objections seriously and test alternative theories with critical experiments,
not merely ones that aim to confirm our prior ideas.

1.4 THE TRANS EFFECT

Ligands, Lt , that are more effective at labilizing any ligand trans to themselves have
a higher trans effect. We see the reason in Sections 4.3 and 4.4, but for the moment
only note that the effect is very marked for Pt(II), and that the highest trans effect
8 INTRODUCTION

ligands either (i) form strong σ bonds, such as Lt = H− or Me− , or (ii) are strong π
acceptors, such as Lt = CO, C2 H4 , or (iii) have polarizable period 3 or higher p block
elements as the donor as in S-bound thiourea, {(NH2 )2 CS or “tu”}.
High trans effect Lt ligands also lengthen and weaken trans M–L bonds, as shown
in X-ray crystallography by an increase in the M–L distance or in nuclear magnetic
resonance (NMR) spectroscopy by a decrease in the M,L coupling (Section 10.4), or
in the infrared (IR) spectrum (Section 10.8) by a decrease in the 𝜈(M–L) stretching
frequency. When Lt changes the ground-state thermodynamic properties of a com-
plex in one of these ways, we use the term trans influence to distinguish the situation
from the trans effect proper in which Lt accelerates the rate of substitution, a kinetic
effect.
To illustrate this, we now move to Pt(II), where the II refers to the +2 oxidation
state (Section 2.4). Pt(II) is four-coordinate and adopts a square planar geometry as
in 1.20. These complexes can react with incoming ligands, Li , to replace an existing
ligand L in a substitution reaction. Where a choice exists between two possible prod-
uct geometries, as in Eqs. (1.3) and (1.4), the outcome is governed by the trans effect.
For example, in the second step of Eq. (1.3), the NH3 does not replace the Cl trans to
NH3 but only the Cl trans to Cl. This means that Cl has a higher trans effect ligand
than NH3 : the Cl effectively weakens the M–NH3 bond. The same holds in Eq. (1.4),
where the NH3 trans to Cl, not the one trans to NH3 , is displaced. This lets us syn-
thesize specific isomers by choosing the right route. This example is also of practical
interest because the cis isomer is a very important antitumor drug (Section 16.6), but
the trans isomer is toxic.

2+

(1.3)

(1.4)

A typical trans effect series for Pt(II) is given here, but the order can change some-
what for different metals, coligands, and oxidation states.