Coordination Chemistry II: Isomers and Coordination Geometries

Coordination Chemistry II:
Isomers and
Coordination Geometries
Chapter 9
Monday, November 16, 2015

A Real World Example of Stuff from Class!
Isomerism
Coordination complexes often have a variety of isomeric forms
Structural Isomers
Molecules with the same numbers of the same atoms,
but in different arrangements.
Isomers generally have distinct physical and chemical properties.
One isomer may be a medicine while another is a poison.
Type 1: Structural isomers differ in how the atoms are connected.

As a result, they have different chemical formulas.
e.g., C3H8O
1-propanol 2-propanol methoxyethane

m.p. -127°C m.p. -89°C m.p. -139°C
b.p. 97°C b.p. 83°C b.p. 8°C
Structural Isomers
Structural (or constitutional) isomers are molecules with the same
kind and number of atoms but with different bond arrangements
In coordination complexes there are four types of structural isomers:

• hydrate (solvent) isomerism occurs when water (or another solvent) can appear
within the primary or secondary coordination sphere of a metal ion
Cr H 2O 6  Cl3 CrCl H 2O 5  Cl2  H 2O

violet crystals blue-green crystals
CrCl2 H 2O 4  Cl  2H 2O CrCl3 H 2O 3   3H 2O
dark green crystals yellow-green crystals
• ionization isomers afford different anions and cations in solution
Co NH 3 5 SO4  NO3  Co NH 3 5 NO3  SO4 
Structural Isomers
In coordination complexes there are four types of structural isomers
• coordination isomerism occurs when ligands can be distributed differently
between two or more metals
• linkage isomerism occurs when a ligand can bind in different ways to a metal
Stereoisomers
The second major class of isomer. Here, the atoms have the same
bonding partners but are arranged differently in 3D space.
Two types: geometrical and optical isomers.

geometrical isomers have ligands at different locations relative to
one another.
' '
ML 4 L 2 ML3 L3
trans cis fac mer

geometrical isomers can occur for octahedral and square
planar but not tetrahedral complexes
Stereoisomers
other examples:
Anti-cancer drug Toxic
cis-2-butene trans-2-butene
Stereoisomers
optical isomers are nonsuperimposable mirror images of each

other.
no rotation
a tetrahedral allows the two
molecule with molecules
four different to be
groups superimposed
mirror
Optical isomers are said to be chiral (not superimposable).
A chiral molecule and its mirror image form a pair of enantiomers.
Each of the enantiomers has handedness (left “L-” or right “D-”).
Chirality
As we discussed in Chapter 4, the easiest way to determine if a
molecule is chiral is to determine its point group:
• if a molecule has only proper rotations it must be chiral
trans,trans-[Fe(NH3)2(H2O)2Cl2] trans,cis-[Fe(NH3)2(H2O)2Cl2] cis,cis-[Fe(NH3)2(H2O)2Cl2]

D2h C2v C1
not chiral not chiral chiral
• application of this rule to compounds with chelating ligands reveals the

importance of rings in the chirality of coordination complexes
C2
chiral
Chelate Ring Conformations
Chelating ligands also impart chirality because of the direction of the
chelate ring.
left-handed screw right-handed screw

(twists counterclockwise (twists clockwise
moving away) moving away)
Λ isomer Δ isomer
Ligand Ring Conformations
For non-planar chelating ligands it is also possible to have different
conformations of the chelate ring.
non-planar
planar
rotate to put the

C–C bond behind the
metal
not chiral
λ isomer δ isomer
keep in mind the barrier to a ring flip is

usually 1-2 kcal mol–1, so the two isomers
will interconvert in solution
Chirality
• Optical isomerism cannot occur in square planar complexes.
• Enantiomeric pairs have identical physical and chemical

properties in nearly every respect.
• Enantiomers will interact differently with other chiral objects, such

as chiral molecules (e.g., proteins) and circularly-polarized light.
• Enantiomers rotate plane-polarized light in opposite directions.

Plane-Polarized Light
Optical Activity
The ability to rotate the plane of polarization of light,

a characteristic property of chiral molecules.
light rotated counterclockwise

optically active • Identically prepared solutions of the
medium two enantiomers of a chiral molecule
(solution of rotate the polarization plane through
chiral molecules) equal angles in opposite directions.
• A mixture of equal amounts of the two

enantiomers (a racemic mixture) or
an achiral substance do not exhibit
this effect.
• Used to study reactions, in optics, and

plane polarized light to measure the concentration of chiral
(light passed through a polarizer) molecules, such as dextrose.
Circularly-Polarized Light
circularly polarized light:
E-field forms a helix, which is a chiral object
clockwise corkscrew motion = right-handed helix
Enantiomers absorb different amounts of left- and right-circularly

polarized light. This is used in circular dichroism spectroscopy.
Coordination Geometries
Factors affecting coordination geometries
1. more bonds = greater stability because a bonding pair of electrons

is lower in energy than an unbonded electron pair
2. d-orbital occupancy – the coordination geometry will adjust to

accommodate non-bonding electron pairs in the d-orbital
manifold
3. sterics – larger ligands favor lower coordination numbers; smaller

ligands favor higher coordination numbers
4. crystal packing effects and solvation effects
VSEPR provides an excellent estimate of coordination geometry for p-

block metals but its fidelity is not as good for transition metals,
lanthanides, and actinides
Coordination Number 1
A very rare coordination number that is known in the gas phase and
for a couple of p-block elements
• also isolable for thallium, but both require this sterically demanding ligand
• must be prepared in the absence of coordinating solvents (NH3, H2O, py, THF,
Et2O, etc)
• once prepared it will readily coordinate other ligands or even bond with other
metal complexes
Known for both sterically contrived environments and for metals with
high d-electron counts (d10)
<2.8 Å
[AuCl2]–
Ag(I), d10 Cu(I), d10 Hg(II), d10
The formula does not always indicate the coordination geometry
TiO2
A somewhat common coordination number for d10 metals or
complexes with bulky ligands
• main group metals (with a lone pair) often adopt trigonal pyramidal
geometries for CN 3
• three-coordinate transition metal complexes are often trigonal
planar
[Au(PPh3)3]+
trigonal planar
D3h
Reactivity is a common theme

for three coordinate
complexes. Reactive
intermediates are often three Mo(NRR′)3
trigonal planar
coordinate species.
D3h or D3d
Four-coordinate complexes are common throughout the Periodic
Table. There are three important four-coordinate geometries:
• tetrahedral
• favored geometry based on sterics only
• minimizes L–L interactions
• ‘normal’ unless there is an electronic reason for another geometry
• see-saw
• primarily observed in p-block metals (e.g., TeCl4 and SF4)
• occurs when central atom has four ligands and one non-bonding electron pair
• square planar
• known for p-block metals with four ligands and two non-bonding electron pairs
• common for transition metals with a d8 electron count and a low spin
configuration: central metal has four non-bonding electron pairs but one pair
resides in dz
2
Another common coordination number with two common geometries
• trigonal bipyramidal
90°
• three equivalent equatorial sites
120°
• two equivalent axial sites
90°
• square pyramidal
• one unique apical ligand
90°
• four equivalent basal ligands
The energy difference between tbp and sq-pyr is usually small and the
rate of interconversion is often fast in solution:
∆G‡ 8-12 kcal mol–1

Very common for transition metal ions.
• octahedral is the basic structure
• all M–L distances equivalent
• all L–M–L angles are 90°
• tetragonal distortion
• axial positions are different than equatorial
• all L–M–L angles still 90°
• trigonal distortion
• change to L–M–L bond angles
• M–L bond distances may or may not be the same
Less common than 4, 5, and 6 coordinate. Occurs with electron-poor
metals and small ligands
• pentagonal bipyramid
• five equatorial ligands and two axial ligands
• capped prismatic structures
e.g., [NbF7]2– e.g., WBr3(CO)4

Coordination Number 8 and Higher
Coordination numbers 8 and higher are uncommon for transition
metals but often observed for lanthanides and actinides
• For CN 8 the most common geometry is the square anti-prism
square anti-prism bicapped

trigonal prism
• higher CNs do not have regular geometric shapes

• typically observed for small chelate ligands such as NO3– and OAc–
e.g., [ReH9]2–
e.g., [Mo(ZnCH3)9(ZnC5Me5)3]

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Coordination Chemistry II:

Monday, November 16, 2015

Type 1: Structural isomers differ in how the atoms are connected.

1-propanol 2-propanol methoxyethane

In coordination complexes there are four types of structural isomers:

Cr H 2O 6  Cl3 CrCl H 2O 5  Cl2  H 2O

• ionization isomers afford different anions and cations in solution

Two types: geometrical and optical isomers.

trans cis fac mer

Anti-cancer drug Toxic

optical isomers are nonsuperimposable mirror images of each

trans,trans-[Fe(NH3)2(H2O)2Cl2] trans,cis-[Fe(NH3)2(H2O)2Cl2] cis,cis-[Fe(NH3)2(H2O)2Cl2]

• application of this rule to compounds with chelating ligands reveals the

left-handed screw right-handed screw

rotate to put the

keep in mind the barrier to a ring flip is

• Optical isomerism cannot occur in square planar complexes.

• Enantiomeric pairs have identical physical and chemical

• Enantiomers will interact differently with other chiral objects, such

• Enantiomers rotate plane-polarized light in opposite directions.

The ability to rotate the plane of polarization of light,

light rotated counterclockwise

• A mixture of equal amounts of the two

• Used to study reactions, in optics, and

clockwise corkscrew motion = right-handed helix

Enantiomers absorb different amounts of left- and right-circularly

1. more bonds = greater stability because a bonding pair of electrons

2. d-orbital occupancy – the coordination geometry will adjust to

3. sterics – larger ligands favor lower coordination numbers; smaller

4. crystal packing effects and solvation effects

VSEPR provides an excellent estimate of coordination geometry for p-

Ag(I), d10 Cu(I), d10 Hg(II), d10

The formula does not always indicate the coordination geometry

Reactivity is a common theme

∆G‡ 8-12 kcal mol–1

• capped prismatic structures

e.g., [NbF7]2– e.g., WBr3(CO)4

square anti-prism bicapped

• higher CNs do not have regular geometric shapes

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