Coordination, What?!

The Complexities of Inorganic

Complexes
 Bonding in Coordination Compounds
• Valence Bond Theory (VBT)
• Crystal Field Theory (CFT)
• Molecular Orbital Theory (MOT)

Valence Bond Theory (VBT)

Lewis bases (ligands)
Lewis acids (metals or metal ions)
The metal utilizes hybridization of metal s, p, and d valence orbitals
to account for the observed structures and magnetic properties of
complexes.
Valence Bond Theory

 Metal or metal ion: Lewis acid

 Ligand: Lewis base
 Hybridization of s, p, d orbitals
C.N. Geometry Hybrids
4 tetrahedral sp3
4 square planar dsp2
5 trigonal bipyramidal dsp3 or sp3d
6 octahedral d2sp3 or sp3d2
Valence Bond Theory

:
Example 1: [Co(NH3)6]3+
Co [Ar] 3d7 4s2
Co3+ [Ar] 3d6

3d 4s 4p 4d

d2sp3
octahedral

if complex is diamagnetic
Valence Bond Theory

Example 2: [CoF6]3–
Co [Ar] 3d7 4s2
Co3+ [Ar] 3d6

3d 4s 4p 4d

4sp3d2
octahedral

if complex is paramagnetic
Valence Bond Theory

Example 3: [PtCl4]2–, diamagnetic

Pt2+ [Xe] 4f14 5d8

5d 6s 6p

dsp2
square planar
Valence Bond Theory

Example 4: [NiCl4]2–, tetrahedral

Ni2+ [Ar] 3d8

3d 4s 4p

4sp3
paramagnetic
Exercises:

Predict the hybridization/geometry of the ff.:

1. [Cr(NH3)6]+3, paramagnetic
2. [CoCl4] -2, paramagnetic
3. [Ni(CN)4]2-, diamagnetic

Predict the magnetic property of the ff.:

1. [Fe(H2O)6]+2 , outer orbital complex

2. [Fe(CN)6]-3, inner orbital complex

Valence Bond Theory (Summary)

 Ligands (Lewis base) form coordinate

covalent bonds with metal center (Lewis
acid)
 Relationship between hybridization,
geometry, and magnetism
 Inadequate explanation for colors of
complex ions
e.g., [Cr(H2O)6]3+, [Cr(H2O)4Cl2]+
Crystal Field Theory (CFT)
1929, Hans Bethe
As originally conceived, it was a model based on a purely
electrostatic interaction between the ligands and the metal ion.
1935, modifications J.H. Van Vleck
allow some
covalency in the interaction

Ligand Field Theory (LFT)

1950, apply CFT to transition metal complexes
successful in interpreting many important
properties of complexes
symmetry consideration identical to
MOT
Crystal Field Theory

 Basis: purely electrostatic interaction

 Spherical field: d orbitals degenerate
spherical field

free ion

What will happen when •

•
six ligands approach from
the six vertices of an •
octahedron? •
•
•
 z
Shapes of d-orbitals
orthogonal

y
d-orbitals have gerade (g) symmetry
x

z
z z y
y
y
x x x

yz xz xy x2-y2 z2

lie between ordinate axes lie along ordinate axes

In a free ion (no ligands), d-orbitals are degenerate ie. they have the same energy)
 Symmetrical ligand field

z2

M
x2-y2

x2-y2 yz z2 xz xy

Energy

x2-y2 yz z2 xz xy

Orbitals are displaced to higher energy by a symmetrical ligand field

destabilised
Effect of ligand field on metal d-orbitals

orbitals forming eg set

orbitals forming t2g set

 Octahedral crystal field splitting

metal ion in symmetrical field in octahedral ligand field

in free space
x2-y2 z2
eg

yz xz xy t2g

x2-y2 yz z2 xz xy

xy, yz, xz stabilised relative to symmetrical field lie between ordinate axes
x2-y2, z2 destabilised relative to symmetrical field lie along ordinate axes
 The difference in energy between the eg and the t2g energy levels is

the crystal field splitting parameter, oct. This is given the value 10 Dq.

symmetrical field octahedral ligand field

eg

o or 10 Dq

t2g

+ 0.6 o = + 6 Dq
eg barycentre
- 0.4 o = - 4 Dq
t2g
 How are electrons added to the
d orbitals?

 d1, d2, d3 - no choice, all in t2g

 d4, d5, d6, d7 - choices

 d8, d9, d10 - no choice, in both t2g and eg

 3+

Electron configurations: d1 ion

e.g. [Ti(OH2)6]3+
violet solution in water
eg
+ 0.6 oct

- 0.4 oct
t2g

one d-electron in a t2g orbital the complex has a

Crystal Field Stabilisation Energy (CFSE) of - 0.4 oct

d2 ions

e.g. [V(OH2)6]3+
eg
+ 0.6 oct

CFSE = - 0.8 oct

- 0.4 oct
t2g

d3 ions

e.g. [Cr(OH2)6]3+ eg
+ 0.6 oct

CFSE = - 1.2 oct

- 0.4 oct
t2g
 High Spin vs Low Spin

 high spin - maximizes # unpaired

electrons

 low spin - minimizes # unpaired electrons

 choice depends on size of o

 High and Low spin Complexes
High spin complex Low spin complex
eg
eg

oct
oct
t2g

t2g

 is small  is large

0.4 oct < P 0.4 oct > P

electrons occupy eg and t2g orbitals electrons pair in t2g oribtals before

singly before pairing occupying eg orbitals

d4 ions
High Spin Complex

eg
+ 0.6 oct CFSE =
3 x - 0.4 oct + 1 x 0.6 oct
t2g - 0.4 oct
= - 0.6 oct

Low Spin Complex

eg

+ 0.6 oct
CFSE =
4 x - 0.4 oct + P
- 0.4 oct = - 1.6 oct + P
t2g

The Pairing Energy P is the energy required to pair two electrons

High Spin vs Low Spin d6

high spin, low spin,

weak field strong field
d8

or

small o large o

no difference in # unpaired electrons

Crystal Field Theory

Factors affecting magnitude of 

1. Oxidation state of the metal ion
-the higher the charge of the metal, the greater
the 

Cation charge cm-1)

divalent 7,500-12,500
trivalent 14,000-25,000
Ex: V(H2O)6+2 – 12,400 cm-1
V(H2O)6+3 – 17,850 cm-1
2. Nature of the metal ion complex  (cm-1)
-  increases on going
[Co(NH3)6]+3 22,900
down from 3d<4d<5d
- higher principal q. no., [Rh(NH3)6]+3 34,100
higher  [Ir(NH3)6]+3 41,000

3. Number and geometry

of the ligands
Δo is 50% larger than Δt
 Spectrochemical Series

4. Nature of the ligands

For a select group of common ligands:

I- < Br- < Cl- < F- < H2O < NH3 < en < NO2- < CN- < CO
weak field strong field

small o large o

Ex.: Complex ion  (cm-1)

[Cr(CN)6]-3 26,600
[Cr(NH3)6]+3 21,600
Crystal Field Theory

Pairing energy (P) vs. O

 If O < P, weak field;
e.g., [Cr(OH2)6]2+

 If O > P, strong field;

e.g., [Cr(CN)6]4–
 Tetrahedral Complexes

Splitting is small.
T  4/9 O

 All tetrahedral complexes are high spin.

 Tetrahedral splitting produces opposite

order of octahedral splitting.
Crystal Field Theory

 Tetrahedral field

t2
t2
e

e
Square Planar Complexes

 another geometry for CN=4

 favored by d8
 [Pt(NH3)2Cl2]
 [Ni(CN)4]2-

 usually low spin

Crystal Field Theory

 Square planar field

SP
Crystal Field Theory (Summary)

 Ligands are point charges

 Metal d electrons repel ligands
 Splitting of d orbitals
 Explanation for colors and magnetism of
complex ions
 No hybridization required
 Color
 Many transition metal coordination
complexes possess color because their
electronic transitions occur in the visible
region of the electromagnetic spectrum.

 usually requires an unfilled d subshell

 complementary colors
The nature of oct
A 490-580 nm
[Ti(OH2)6]3+
h

 / nm

eg eg
h
o

t2g t2g

Absorption spectrum: max = 510 nm = 243 kJ mol-1

Light Absorption for [Ti(H2O)6]3+

 [Ti(H2O)6]3+ is red-violet
Splittings for Several CrIIIIII Complexes

 increases
 Color and the
Spectrochemical Series

 Name the compound K4[MnF6].

You do it!
potassium hexafluoromanaganate (II)
 What are its geometry, magnetic properties, and
hybridization at Mn?
You do it!
 The 6 fluoride ions are in an octahedral geometry.
 There will be 5 unpaired electrons in a high spin
complex.
 The Mn atom has sp3d2 hybrid orbitals.
 Color and the
Spectrochemical Series

 Name the compound [Mn(NH3)6]Cl2.

You do it!
manganese (II) hexaamminechloride
 What are its geometry, magnetic properties, and
hybridization at Mn?
You do it!
 The 6 ammonia molecules are in an octahedral geometry.
 There will be 1 unpaired electron in a low spin complex
 The Mn atom is d2sp3 hybridized.