Electronic spectra of transition metal complexes

Characteristics of electronic spectra

a) Wavelength

Energy of electronic transition

b) Shape.

Gaussian Band Shape - coupling of electronic and

vibrational states

c) Intensity.

Molar absorptivity, (M1cm1) due to probability

of electronic transitions.

d) Number of bands

Transitions between States of given dn configuration.

Band intensity in electronic spectra ()

Electronic transitions are controlled by quantum mechanical selection rules
which determine the probability (intensity) of the transition.
Transition
Spin and Symmetry forbidden "d-d" bands
Spin allowed and Symmetry forbidden "d-d" bands

Spin and Symmetry allowed LMCT and MLCT bands

max (M1cm1)
0.02 - 1
(Oh) 1 - 10
(Td) 10 103
103 - 5 x 104

Spin Selection Rule: There must be no change in the spin multiplicity (2S + 1)
during the transition.
i.e. the spin of the electron must not change during the transition.
Symmetry (Laporte) Selection Rule: There must be a change in parity (g u)
during the transition
Since s and d orbitals are g (gerade) and p orbitals are u(ungerade), only
s p and p d transitions are allowed and d d transition are formally
forbidden. [i.e. only transitions for which l = 1 are allowed].
d d bands are allowed to the extent that the starting or terminal level of
the transition is not a pure d-orbital. (i.e. it is a molecular orbital of the
complex with both metal and ligand character).

States for dn configurations

Russel-Saunders Coupling
Angular momentum of individual electrons couple to give total angular
momentum for dn configuration ML = ml
Spin momentum of individual electron spins couple together to give total
spin, S = s
Inter-electronic repulsions between the electrons in the d orbitals give rise to
ground state and excited states for dn configurations.
States are labeled with Tern Symbols
Electonic transitions between ground and excited states are summarized in
Orgel and Tanabe-Sugano diagrams .
Term Symbols (labels for states) contain information about L and S for state
Hunds Rules. i) Ground state has maximum spin, S
ii) For states of same spin, ground state has maximum L.

Number of d-d bands in electronic spectrum

Excitation from ground state to excited stated of dn configuration
Ground State

Triple degeneracy of a d2 ions 3T2g

ground state due to three possible sites
for hole in t2g level

Singly degenerate 3T2g ground state.

Only one possible arrangement for
three electrons in t2g level

Triple degenerate ground state for d7

Three possible sites for hole in t2g level

Singly degenerate 3T2g ground state.

Only one possible arrangement for
six t2g electrons.

d2

eg
t2g

eg
3

t2g

eg
7

t2g

eg
8

t2g

Excited States

Labeling of d-d bands in electronic spectrum.

Consider states of dn configuration

Determine free ion ground state Term Symbol (labels for

states)

Assign splitting of states in ligand field

Spectroscopic labeling of bands.

Orgel diagrams (high-spin)

Tanabe-Sugano diagrams (high-spin and low-spin)

Individual electron l = 2,
-1, -2
Maximum ml = l

ml = 2, 1, 0,

l =
0, 1, 2, 3,
Orbital: s, p, d , f
_______________________________
dn configuration, L = 0, 1, 2, 3, 4
Term Symbol
S, P, D, F, G
ML = m l ,

maximum ML = L

Spin Multiplicity = 2 S +1

Free ion ground state Term Symbols for dn configurations

Term Symbols (labels for states) contain information about L and S for ground state

Hunds Rules.
maximum
L =i)MGround
ML has
= m
S = sspin, S
L (max) state
l
-1 state
-2 has maximum L
l =ii)2, For
mlstates
=
1 spin,
0 ground
2 of same
Term
L
S 2S + 1 symbol
2

1/2

3 3/2

5/2

Splitting of the weak field dn ground state terms in an

octahedral ligand field

Ground state determined by inspection of degeneracy of terms for given dn

Orgel Diagrams

Eg

P
3

D
2

d1
2

T2g

Ti3+

d2
Eg

A2g

T2g

T2g

T1g(P)

T1g

T1g

P
4

T1g

T2g

T2g

D
5

d3
3

o
A2g

Eg

d 4 o

T2g

A2g
3

2+

T1g(P)

T1g

T1g

T1g(P)

Cr3+

Mn3+

The d-d bands of the d 2 ion [V(H2O) 6]3+

(a) [Ni(H20)6]2+

(b) [Ni(NH3)6]2+

Racah Inter-electronic Repulsion Parameters (B, C)

1

E(3P) = A+7B

E(1D) = A - 3B + 2C

E(3F) = A - 8B

d2

= 15B

= 5B + 2C

The Tanabe-Sugano diagram for the d2 ion

Evidence for covalent bonding in metal-ligand interactions

The Nephelauxetic Effect (cloud expansion)
Reduction in electron-electron repulsion upon complex formation
Racah Parameter, B: electron-elctronic repulsion parameter
Bo is the inter- electronic repulsion in the gaseous Mn+ ion.
B is the inter- electronic repulsion in the complexed MLxn+ ion.
The smaller values for B in the complex compared to free gaseous ion is
taken as evidence of smaller inter-electronic repulsion in the complex due to
a larger molecular orbital on account of overlap
of ligand and metal orbital, i.e. evidence of covalency (cloud expansion).
Nephelauxetic Ratio, = B
Bo

Nephelauxetic Effect
Nephelauxetic Ligand Series
I < Br < CN < Cl < NCS < C2O42- < en < NH3 < H2O < F
Small
Covalent

Large
Ionic

Nephelauxetic Metal Series

Pt4+ < Co3+ < Rh3+~Ir3+ < Fe3+ < Cr3+ < Ni2+ < V4+< Pt2+~ Mn2+
Small

Large

Large overlap

Small overlap

Covalent

Ionic

Empirical Racah parameters, h, k

= 1 [h(ligand) x k(metal)]
Cr(NH3)63+

= 1 hk
= 1 (1.4)(0.21)
= 0.706

Cr(CN)63-

= 1 hk
= 1 (2.0)(0.21)
= 0.580
Bo - B = hligands x kmetal ion
Bo

Typical o and max values for octahedral (ML6) d-block metal complexes

_________________________________________________________________
_
Complex
o cm-1
~ max (nm)
Complex
o cm-1
max
(nm)
___________________________________________________________________________________
[Ti(H2O)6]3+
20,300
493
[Fe(H2O)6]2+
9,400
1064
3+
3+
[V(H2O)6]
20,300
493
[Fe(H2O)6]
13,700
730
2+
3[V(H2O)6]
12,400
806
[Fe(CN)6]
35,000
286
34[CrF6]
15,000
667
[Fe(CN)6]
33,800
296
3+
3[Co(H2O)6] , l.s. 20,700
483
[Fe(C2O4)3]
14,100
709
2+
3[Cr(H2O)6]
14,100
709
[Co(CN)6] l.s.
34,800
287
3+
3+
[Cr(H2O)6]
17,400
575
[Co(NH3)6] l.s. 22,900
437
3+
2+
[Cr(NH3)6]
21,600
463
[Ni(H2O)6]
8,500
1176
[Cr(en)3]3+
21,900
457
[Ni(NH3)6]2+
10,800
926
32+
[Cr(CN)6]
26,600
376
[Ni(en)3]
11,500
870
___________________________________________________________________________________

1.

Assign the metal oxidation state in the following compounds.

a.
b.
c.

K2[PtCl6]
Na2[Fe(CO)4]
[Mn(CH3)(CO)5]

2.

Account for the following:

The manganous ion, [Mn(H2O)6]2+, reacts with CN- to form [Mn(CN)6]4- which

has

= 1.95 B.M., but with I- to give [MnI4]2- which has = 5.93 B. M.

[Co(NH3)6]Cl3 is diamagnetic, whereas Na3[CoF6] is paramagnetic ( = 5.02

B.M).
[PtBr2Cl2]2 is diamagnetic and exists in two isomeric forms, whereas
[NiBr2Cl2]2
has a magnetic moment, = 3.95 B.M., and does not exhibit isomerism.
Copper(II) complexes are typically blue with one visible absorption band in
their
electronic spectra whereas copper(I) complexes are generally colorless.
Assign a spectroscopic label to the Cu2+ transition.