Molecular Orbital Theory of

Coordination Compounds

- Huheey, Keiter & Keiter, Inorganic Chemistry, 4th Edn

- F.A. Cotton, Chemical Application of Group Theory

Crystal Field Theory

Explain reasonably the electronic spectra and magnetism of TM complexes.

The interaction b/w metal and ligand is purely electrostatic (no covalency!)

Evidences for covalent character:

Nephelauxetic effect:

e-e repulsion in complexes is somewhat

less than that in a free ion

Electron paramagnetic resonance (EPR)

spectroscopy: hyperfine splitting pattern

Molecular Orbital Theory

In Molecular Orbital Theory:
Orbital structure of molecules Shapes & energy order of MOs.

Linear Combination of Atomic Orbitals (LCAO):

c
i i
i

Shape of MOs are determined by the cs (both magnitude & sign).

(e.g. Variation Theorem Solve Secular equations)
N
( H jk i S jk ) cki 0,
k 1

j 1,2, , N

Electronic structures are obtained by placing electrons in the MOs

(starting with the lowest one).
Construction of MOs: Decompose the system into two or more simple
subsystem whose orbitals (atomic or molecular) are known. Then allow
the orbital of the fragments to interact (LCAO).
Interaction between two orbitals:
Role of symmetry:

Interactions between two orbitals

Same type

Different types

,1
1

1 2

2(1 S12 )

; E H11

S2
E E

E E S 1* 2 d

, 2
2

H12 H11S12
1 S12

In order to have non-zero S, orbitals must be bases for the same irreducible
representation of the molecular symmetry group, i.e. they must have same
symmetry, ONLY ORBITALS OF SAME SYMMETRY INTERACT.

MO Theory of Transition metal complexes

s, p electrons: minimum 24 orbitals

Results with NN Secular matrix;
N = 33 (minimum)

nd, (n+1)s, (n+1)p : minimum 9 orbitals

l l m m p p

Role of Symmetry in Bonding

e.g. Water:

Participating orbitals: O: 2s, 2p; H: 1s

6 6 Secular matrix

To construct the MOs for an AXn molecule, we need to combine the atomic orbitals on X
and then match the resultant combinations with the atomic orbitals of the central atom A.
With Group Theory, we can derive the linear combinations systematically.

1. Determine the symmetries of participating orbitals:

A1 : s, pz ; B1 : px ; B2 : p y

2. Determine the characters of representation:

Reduction Formula:

1
ai ( Rk ) ( R )n( R )
i k
k
hk

Symmetry Adopted Linear Combination

3. Determine the linear combination with appropriate symmetry:

(ii) By Inspection

(i) Projection Operator:

P [ (R )R ]
i k k
k

SUMMARY

Symmetry

Orbitals on O

Orbitals on H

MO

A1

2s, 2Pz

1sa+1sb

1a1, 2a1, 3a1

B2

2Py

1b2

B1

2Px

1sa-1sb

1b1, 2b1

Formation of MOs in H2O

Sym
metry

Orbitals
on O

Orbitals
on H

MO

A1

2s, 2Pz

1sa+1sb

1a1, 2a1, 3a1

2py, b2

2pz, a1
B2

2Py

1b2

B1

2Px

1sa-1sb

1b1, 2b1
2px, b1

2s, a1

MO Diagram for H2O

2p

1sa - 1sb
1sa + 1sb

2s

MOTof Transition metal complexes

L
I
G
A
N
D
S

Metal

Variation principle:

N
( F jk i S jk ) aki 0,
k 1

j 1,2, , N

Octahedral ML6 Sigma Bonding

(s; p , p , p ; d
,d )
x y z x2 y 2 z 2

P [ (R )R ]
A. Finding SALC by Projection Operator Method:
i k k
k
a
P 1 (L ) ~ 4(L L L L L L )
1
1 2 3 4 5 6

Determination of SALCs
a 1 (L L L L L L )
6 1

1g

a1g

e(1) 1 (2L 2L L L L L )
g

12

t(1) 1 (L L )
1u

2 1

e(2) 1 (L L L L )

t(2) 1 (L L )
1u

2 3

4 3

t(3) 1 (L L )
1u

2 5

eg

t1u

A -bond MO Diagram of Octahedral ML6

Example:
[Co(NH3)6]3+
18e: diamagnetic

[CoF6]318e: paramagnetic ??

Tetrahedral ML4 Sigma Bonding

Tetrahedral ML4 Sigma Bonding: MOs

[CoCl4]215e: paramagnetic

Sq. Planar ML4 Sigma Bonding

Sq. Planar ML4 Sigma Bonding: MOs

Typical for d8 ion:

16e: diamagnetic

Octahedral ML6 Pi- Bonding

Octahedral ML6 Pi- Bonding

Metal Complexes with Ligands containing orbitals

Octahedral ML6 Pi- Bonding: SALCs

t2g

Effect of Pi-bonding in MOs

Additional t2g

Example: [CoF6]3LGOs constructed

from 2p (F) orbitals

Pi- Bonding & MO Theory

MO diagram for Pi-donor ligands

MO diagram for Pi-acceptor ligands

Importance of - Bonding:
Explaining the Spectrochemical Series
Determining patterns in ligand substitution reaction
Reactivity & stability of organometallics

Evidences for Pi Bonding: Metal Carbonyls

Bonding Model: -donor (OC M) and a -acceptor (OC M)

Crystallography:
Greater -bonding
longer C O bond,
shorter M C bond
Longer C O bond than the normal CO in
free CO (112.8 pm) could be taken as
evidence for bonding. However, M C
bond length gives better indication!

Example: Re(CH3)(CO)5

Re CO length: 200.4 pm (24 pm shorter than corresponding

-only bond.

Evidences for Pi Bonding: Metal Carbonyls

Phosphine & Phosphite Derivatives of Cr(CO)6

Evidences for Pi Bonding: Metal Carbonyls

IR Spectroscopy: (CO stretching frequency very useful)
HOMO (3) LUMO (2) causes the C O stretching frequency to drop from
2143 to 1489 cm-1.

Favored by system with

positive charge
accumulated on M

Favored by system with

negative charge which
enhances back
donation.

So, net charge on carbonyl compounds have a

profound effect on CO stretching frequency.

Greater -ve charge on M Stronger -Bonding Weaker C O bond

Lower IR frequency

Photoelectron Spectroscopy: Cr(CO)6

Removal of electron from t2g orbital should weaken
the M C bond and decrease MC

MC for Cr(CO)6 ion is 325 cm-1 (379 cm-1 for

neutral) corresponds to 14 pm increase in M C
length on ionization

MO Theory of Metallocenes
Chapter 15: Huhee
Chapter 7: Cotton

Sandwich Compounds: Metallocenes

Complexes in which a metal atom is found between two parallel carbocyclic rings:
Sandwich compounds. Metal-ligand bond b/w a metal & the orbitals of C5H5.

Metallocenes & 18-electron rule: usually do not obey

SALCs of ferrocenes

Molecular Orbitals of Cp-

Molecular Orbitals of Cp-

a1

e1

e2

Molecular Orbitals of cycloalkenes

SALCs of [CpCp]2-

Molecular Orbitals of ferrocenes

Molecular Orbital diagram of metallocenes

Structures of Cyclopentadienyl Compounds