Graduate Center

Inorganic Chemistry
(Fall 2012)

Unit 5
Coordination Chemistry

Part 4
Electronic spectra of Coordination Chemistry
Suggested reading:
Miessler & Tarr: Chapter 11

Electronic spectra of coordination

complexes

Most striking aspect of many TM coordination compounds is their vivid

colors
The UV and vis spectra of coord. compounds involve e- transitions between
the d orbitals of the metals
How are the energies of these orbitals and the possible ways in which ecan be raised from lower to higher energy levels
Energy levels of d e- configurations more complicated than expected
For many coord. compounds the electronic absorption spectrum provides a
convenient method for determining the magnitude of the effect of ligands
on the d orbitals of the metal
Although any geometry can be studied we will focus on octahedral
complexes and we will examine how the absorption spectrum can be
used to determine o for a variety of complexes

Electronic spectra (UV-vis spectroscopy)

Spectra commonly
obtained as plots of
absorbance
vs wave length

Electronic spectra (UV-vis spectroscopy)

Absorption
of light

The colors of metal complexes

[Cu(H2O)6]2+

Quantum numbers (Electronic configurations )of multi-electron atoms

What is a 2p2 configuration?
n = 2; l = 1; ml = -1, 0, +1; ms = 1/2

Many configurations fit that description

These configurations are called microstates

and they have different energies
because of inter-electronic repulsions

Electronic configurations of multi-electron atoms

Russell-Saunders (or LS) coupling
(interactions between the orbital angular momenta and the spin angular
momenta from each electron produce this coupling and atomic
states called microstates that can be described by new quantum numbers)

For each 2p electron

n = 2; l = 1
ml = -1, 0, +1
ms = 1/2

For the multi-electron atom

L = total orbital angular momentum quantum number
S = total spin angular momentum quantum number
Spin multiplicity = 2S+1
ML = ml
MS = ms

(-L,0,+L)
(S, S-1, ,0,-S)

ML/MS define microstates and L/S

define states (collections of microstates)
Groups of microstates with the same
energy are called terms

Determining the microstates for p2

a) No 2 e- in same microstate have

identical quantum numbers (Pauli)
b) Count only unique microstates

Notations:
1st e- ml = +1, ms = +1/2 1+
2nd e- ml = 0, ms = -1/2 0-

Microstate: 1+0-

L and S largest
possible values
for ML and MS

L,S and J describe the energy and symmetry of an atom or ion and determine
the possible transitions between states of different energy

Spin multiplicity 2S + 1

Determining the values of L, ML, S, Ms for different terms

1S

2P

2 e-

1 e-

Classifying the microstates for p2

Largest ML is +2,
so L = 2 (a D term)
and MS = 0 for ML = +2,
2S +1 = 1 (S = 0)
1D
Next largest ML is +1,
so L = 1 (a P term)
and MS = 0, 1 for ML = +1,
2S +1 = 3
3P

Spin multiplicity = # columns of microstates

One remaining microstate

ML is 0, L = 0 (an S term)
and MS = 0 for ML = 0,
2S +1 = 1
1S

Largest ML is +2,
so L = 2 (a D term)
and MS = 0 for ML = +2,
2S +1 = 1 (S = 0)
1D

Next largest ML is +1,

so L = 1 (a P term)
and MS = 0, 1 for ML = +1,
2S +1 = 3
3P
ML is 0, L = 0
2S +1 = 1
1S

Energy of terms (Hunds rules)

Lowest energy (ground term)

Highest spin multiplicity
3P term for p2 case
3P

has S = 1, L = 1

If two states have

the same maximum spin multiplicity
Ground term is that of highest L

Lets try now to determine the microstates for s1p1

Determining the microstates for s1p1

Careful
these terms
are now ok
s1p1!
They are not
duplicated here

Determining the terms for s1p1

Ground-state term
Remember for determining terms we go to largest ML value, then second largest
ML value and more only when needed

Electronic configurations of multi-electron atoms

Russell-Saunders (or LS) coupling

For each 2p electron

n = 1; l = 1
ml = -1, 0, +1
ms = 1/2

For the multi-electron atom

L = total orbital angular momentum quantum number
S = total spin angular momentum quantum number
Spin multiplicity = 2S+1
ML = ml (-L,0,+L)
MS = ms (S, S-1, ,0,-S)

ML/MS define microstates and L/S

define states (collections of microstates)
Groups of microstates with the same
energy are called terms

Summarizing:
p2
ML & MS
Microstate
Table
States (S, P, D)
Spin multiplicity
Terms
3P, 1D, 1S

Ground state term

3P

Spin-orbit coupling
To this point of discussion of multielectron atoms, the spin and
orbital angular momenta have been treated separately
The spin and angular momenta couple with each-other: spinorbit coupling
In multielectron atoms, the S and L quantum numbers combine
into the total angular momentum quantum number: J
J = L + S, L + S -1, L + S -2, [L S]
Spin-orbit coupling acts to split free-ion terms into states of
different energies

The 3P term therefore splits into states of 3 different energies, and the total energy
level diagram for the carbon atom:
Energy (cm-1)
21648.8
10193.7
43.5
16.4
0

So, spin-orbit coupling generates 5 energy states for the carbon atom. The state of the
lowest energy (spin-orbit coupling included) can be predicted from Hunds third rule:
For subshells (such as p2) that are less than half-filled, the state having the lowest J value
has the lowest energy (e.g. here 3Po); for sub-shells that are more than half-filled, the state
having the highest J value has the lowest energy. Half-filled subshells have only one
possible J value.

For metal complexes we need to consider

d1-d10
d2
3F, 3P, 1G, 1D, 1S

For 3 or more electrons, this is a long tedious process

But luckily this has been tabulated before

In the interpretation of spectra of coordination

compounds, it is often important to identify the
lowest-energy term
d3

1. Sketch energy levels, showing d e2. Spin multiplicity of lowest-energy state = # unpaired e- + 1 = 4
3. Determine the maximum possible value of ML (ml) for the
configuration as shown. This determines the type of free-ion term
(as they are unpaired ms = 1/2 for all or -1/2 so ml = 2, 1, 0; 2 + 1 + 0
= 3)
4. Combine 2 and 3 to get ground term: 4F

What about d4 (low spin)?

d4

1. Sketch energy levels, showing d e2. Spin multiplicity of lowest-energy state = #

unpaired e- + 1 = 3
3. Determine the maximum possible value of
ML (ml) for the configuration as shown. This
determines the type of free-ion term (2 + 2 + 1
+ 0 = 5)
4. Combine 2 and 3 to get ground term: 3H

Note that here ml = 2 for the first 2 e- does not violate the exclusion
principle, because the e- have opposite spins

Transitions between electronic terms will give rise to spectra

Selection rules
(determine intensities)
Laporte rule
g g forbidden (that is, d-d forbidden)
but g u allowed (that is, d-p allowed)

Spin rule
Transitions between states of different multiplicities forbidden
Transitions between states of same multiplicities allowed

These rules are relaxed by molecular vibrations, and spin-orbit coupling

-Vibrations may temporarily change the symmetry (not Oh, center of symmetry temporarily lost)
-Td complexes absorb strongly (combination of sp3 and sd3 hybridization of the metal orbitals,
p contribution)
- Spin-orbit coupling (splitting of free-ion terms, e.g. 3P splits into 3 3PJ states of different energy)

Very useful if we can relate the electronic

spectra of transition metal complexes to the
ligand field splitting (o) for Oh complexes!
To do so we need two types of diagrams:
- Correlation diagrams
- Tanabe-Sugano diagrams
Both make use of group theory since Free-Ion Terms and Strong-Field States have
symmetry characteristics that enable them to be reduced to their constituent irreducible
representations

Group theory analysis of term splitting

d2
Excited state eg2

Excited state t2geg

3F, 3P, 1G, 1D, 1S

Ground state t2g2

No ligand field

Real complexes

Effect of ligands so strong that it completely

overrides effects of LS coupling

Tanabe-Sugano diagrams

Lowest-energy state plotted

along the horizontal axis

B Racah parameter
repulsion between
terms same 2S+1

Electronic transitions and spectra

Other configurations
d3
d9

d1

d2

d8

Other configurations

d3

The limit between

high spin and low spin

Determining o from spectra

d1

d9

One transition allowed of energy o

Determining o from spectra

mixing

mixing

Lowest energy transition = o

Ground state is mixing

(E T1gA2g) - (E T1gT2g) = o

The d5 case

All possible transitions forbidden

Very weak signals due only to
spin-forbbiden transitions, faint color

Some examples of spectra

Analysis of d4, d6 and d7

very difficult as there are
many excited states of the
same multiplicity as the
ground state

Charge transfer spectra

Much more intense bands

Metal character

LMCT
Formal reduction of the metal
donor ligands

Ligand character

Ligand character

MLCT
Metal character

Formal oxidation of the metal

acceptor ligands (CO, CN-, SCN-,
bipy, S2CNR2-)

Chem 76/76.1/710GConcepts and skills Unit 5

Main concepts
Nomenclature of coordination and organometallic
complexes
Isomerism in coordination and organometallic complexes
Crystal field, ligand field and MO theory of metal
complexes: crystal field and ligand field splitting, high
spin and low spin complexes and the spectrochemical
series, spin-only magnetic moments
MO diagram for octahedral complexes, -bonding and
bonding
Jahn-Teller effect and distortions
The square-planar configuration/MO diagram (crystal
field approach)
Substitution reaction mechanisms in octahedral and
square planar complexes
Trans effect
Basic mechanisms of electron transfer reactions (outer
and inner sphere).

Main skills
To provide the name of a complex given the formula or the formula
given the name
To determine the possible isomers in 4- 5- and 6-coordinated
complexes, including enantiomers
To identify d orbitals and to visualize them in space
To explain the splitting of d orbitals by a tetrahedral or an
octahedral field
To distinguish electron configurations in high spin and low spin
complexes, to calculate magnetic moments (spin-only) and ligand
field stabilization energies
To predict the occurrence of Jahn-Teller distortions from electron
configurations
To distinguish dissociative and associative mechanisms on the
basis of kinetic evidence
To predict reaction products based on trans effects
To describe inner-sphere and outer-sphere electron transfer
reactions.

Electronic terms and electronic spectra in metal

complexes. Tanabe-Sugano diagrams.

To interpret simple electronic spectra of complexes using TanabeSugano diagrams.