Bonding Theories of Transition Metal comlexes

(Coordination compounds)
1) Valency bond theory (VBT) (Pauling 1930)
 L to M dative bond, can not explain color (co-ordinate covalent
bond)
 Can explain magnetic behavior but not temperature dependent
magnetic behavior
2) Crystal Field Theory (Bethe 1929)
 Coulomb Interactions/ ionic bond rather than covalent bond
 Attraction between metal ion and ligand electrons
 Repulsion between metal electrons and ligand electrons
 Can account the color, and temperature dependent magnetic
behavior
Adjusted crystal field theory (ACFT; Van Vleck 1935)
(MO Theory) Overlap of orbitals between ligands and metal
 Crystal Field Theory (CFT)
Consequence of metal ligand repulsion

 The d-orbitals of a free metal ion are degenerate (i.e., the

energy levels are same).
 There is an increase in the energy of d- orbitals due to the
repulsion caused by the incoming ligands.
 The magnitude of the increase in energy is NOT equal for all
the five orbitals. Thus the d- orbitals in the complexed metal
ion are NOT equally energetic i.e., non-degenerate.
 Orbitals
An atomic orbital is a mathematical function that describes the
wave-like behavior of either one electron or a pair of electrons in an
atom. This function can be used to calculate the probability of
finding any electron of an atom in any specific region around the
atom's nucleus.

s- orbital

p- orbitals
 d- orbitals
Degenerate (carries same energy) in a free metal ion/atom

t2g

eg

(comes from spectroscopy

and quantum mechanics)
Five d-orbitals with combination diagram
showing how they fit together
Octahedral Complexes
The energy of d-orbitals in presence of octahedral crystal field

(Energy conservation law)

 Crystal Field Splitting Energy or
Crystal Field Stabilization Energy
(CFSE):
The separation between the two sets of orbitals, t2g and eg, is CFSE
 Ligands effect on CFSE is given by the spectrochemical series (a
list of ligands in order of ligand-field strength)
 Ligands with strong pi-acceptor (plus sigma-donor) capabilities are
strong-field ligands (e.g., CO)
 Ligands with pi-donor abilities (halides) are weak-field ligands and
others with pure sigma-donor (NH3, H2O) capability are moderate-
field ligands
(sigma donors)
Basicaly all ligands are sigma donors but some of them can be pi
donors/acceptors in addition.

How can you tell

 a) has only 1 electron pair at coordinating atom? sigma donor
 b) has more than 1 electron pair at coordinating atom? sigma and pi
donor
 c) has double or triple bond at coordinating atom? sigma donor and
pi acceptor
 d) If the ligand coordinating by phosphorous? sigma donor and d
acceptor
Do increases with increasing oxidation number of the metal. This is due to the
smaller size of the ion, resulting in smaller metal to ligand distances, and hence,
a greater ligand field.
Do increases as you go down a group. This is due to the better bonding ability
of expanded shells using the 4d or 5d orbitals.

1st row TM 2nd row TM 3rd row TM

 High-spin and low-spin complexes (octahedral)
d1-d3 : Metals-ion systems, Hund’s rule predicts that electrons will
not pair until all the t2g (degenerate) orbitals are equally occupied

D4- d7:
Electron configurations can in principle be in high- or low-spin states

d4 system: the fourth electron has two options, it can go in an eg

orbital so all four electrons are occupying orbitals singly; this is high-
spin (HS d4). Or it could go into a t2g orbital where it will pair up with
another electron; this is low-spin (LS d4)
d5 system:

d6 system:

D8-d10 has only one

type of possibility.

d7 system:
D4- d7: high- or low-spin configuration?

(i) Crystal Field Splitting Energy (Δo)

(ii) Pairing energy (P) (The spin-pairing energy (P) is the increase
in energy that occurs when an electron is added to an already
occupied orbital)

When the Δo < P: a high-spin configuration occurs which produces

complexes with the maximum number of unpaired electron spins

When Δo > P: a low-spin configuration occurs which produces

complexes with the minimum number of unpaired electron spins
 Crystal Field Stabilization Energy
CFSE for octahedral complexes can be calculated
using the following equation

CFSE = {-0.4 x n(t2g) + 0.6 x n(eg)}Do + mP

Where,
n(t2g) = number of electrons in t2g orbitals

n(eg) = number of electrons in eg orbitals

m = number of paired electron pairs (excluding natural pairing)
P = pairing energy
Calculated CFSE values for metal-ions with d 1-d10 electron configuration
Calculated CFSE values for metal-ions with d 1-d10 electron configuration
Calculated CFSE values for metal-ions with d 1-d10 electron configuration
Calculated CFSE values for metal-ions with d 1-d10 electron configuration
Calculated CFSE values for metal-ions with d 1-d10 electron configuration
For select metal complexes, the following Table lists values of
pairing energy (P), Do, CFSE and resulting spin-state
 The effects of ligand type, oxidation state of the metal and position of the metal
(3d, 4d or 5d) on the magnitude of the CFSE values are illustrated in Table

Accordingly, the octahedral Mn(II) complex with Cl - as a ligand (weak-field) has

lesser stabilization energy (7,500 cm-1) as compared to the same complex with
CN- (strong-field), which is four-times greater (30,000 cm-1), thus making it low-
spin.
On the other-hand, Co(III) complexes with almost all the ligands (except F -;
[CoF6]3- is high-spin) are low-spin because of +3 oxidation state; Similarly, the
analogous Rh(III) complexes are all low-spin because the metal, Rh is in 4d
series.
t2g-orbitals are repelled
more than eg orbitals
(reversal of Octaherdal)