Coordination Chemistry II: Theories of Electronic Structure: Friday, November 20, 2015

Coordination Chemistry II:
Theories of Electronic Structure

Chapter 10
Friday, November 20, 2015

Experimental Evidence for Electronic Structure
Electronic structure models seek to explain (and predict) the trends in
experimental data that are observed for coordination complexes
• Thermodynamic data – formation constants reflect relative M–L bond strengths
• Magnetic moment – coordination complexes often have unpaired electrons, which

lead to measurable magnetic moments
• Electronic spectra – UV-Vis spectroscopy probes electronic transitions between

electronic states of different energy
• Coordination number and geometry – in coordination complexes the observed

geometries are often strongly influenced by subtle electronic structural
considerations in addition to sterics and the number of non-bonding electron pairs
(VSEPR considerations)
Theories of Electronic Structure
Over the years electronic structural theories have become more and
more sophisticated.
• Valence Bond Theory – uses hybrid orbitals, Lewis dot structures, and VSEPR to
understand and predict the electronic structure of simple molecules
• Molecular Orbital Theory – assumes that the valence electrons of a molecule are
shared by all nuclei in the molecule, forming molecular orbitals analogous to the
atomic orbitals of individual atoms
• Crystal Field Theory – an electrostatic approach to understanding the electronic

spectroscopy of crystals – metal valence electrons are perturbed by negative point
charges arranged in a regular coordination geometry – no description of M–L
bonding
• Ligand Field Theory – combines ideas of crystal field theory and molecular orbital
theory to describe the interactions of metal valence orbitals with frontier MOs of the
ligands
• Angular Overlap Method – an empirical method for estimating the relative frontier
orbital energies in LFT calculations by accounting for the relative orientation of the
metal and ligand orbitals
Electronic Structure of Complexes
Metal complexes are often brilliantly colored and/or paramagnetic.

These properties result from the electronic structure of the complexes.
Co(NO3)2 K2CrO4 CuSO4

K2Cr2O7 NiCl2 KMnO4
• Crystal Field Theory (simple electrostatic model)

• Ligand Field Theory (more accurate MO model)
Transition Metals
• The transition elements are those elements with partially

filled d-orbitals. Groups 3 through 11.
• These elements are all metals → transition metals.
• Partially filled d-orbitals responsible for color and magnetism.
375
Origin of Color in Complexes
Color arises from electronic transitions involving d-orbitals.

- color depends on metal and ligand(s) combination.
Metals with totally empty/full d-orbitals are colorless.
d0 d0 d0 d0 d10
Transition metals with partially filled d-orbitals have color.
d3 d6 d7 d8 d9
Crystal Field Theory
Simple electrostatic theory to explain the color and magnetism

of transition metal complexes.
400 500 600 800

Transition Metal Gems
Many gemstones owe their color to transition metal ions
Corundum (Al2O3): Colorless

Cr → Al : Ruby
Mn → Al: Amethyst
Fe → Al: Topaz
Ti & Co → Al: Sapphire
Beryl (Be3Al2Si6O18): Colorless
Cr → Al: Emerald
Fe → Al: Aquamarine
CFT was originally developed to explain the colors of these crystals.

• Basic idea: ligands act as point negative charges, and the

energy of electrons in the metal orbitals depends on the
amount of electrostatic repulsion with ligands.
• Factor #1: Metal (usually positive) is stabilized by bonding to
negative ligands to form complex.
• Factor #2: The d-orbitals have different shapes. Electrons in
the d-orbitals are repelled to different degrees by the ligands.
The five d-orbitals will split in the crystal field.
in an octahedral field: eg
CF
z2 x2–y2
Δo splitting
energy
t2g
xy xz yz
CFT Energetics
i) Separated metal and i

ligands → high energy
ii) Coordinated metal

complex → stabilized
iii) Include ligand-d electron iv
repulsion
→ isotropic destabilization iii
iv) Include orbital shapes
→ degeneracy lifted ii
Field Splitting of d-Orbitals
octahedral field
The degeneracy of the

d-orbitals is lifted.
eg
d-orbitals pointing directly at ligands
experience more electrostatic repulsion
and are destabilized (higher energy)
energy (including electron- t2g

ligand repulsions) before d-orbitals pointing between the ligands
accounting for orbital shapes experience less electrostatic repulsion
and are stabilized (lower energy)
Field Splitting of d-Orbitals
octahedral crystal field splitting diagram
eg
0.6Δo
Energy
dxy dxz dyz dz2 dx 2- y2 Δo

Barycenter 0.4Δo
(isotropic field) t2g
octahedral field
• The Barycenter is the average energy of the d-orbitals.

Three orbitals stabilized by 0.4Δo = -1.2Δo. energy
Two orbitals destabilized by 0.6Δo = 1.2Δo. conserved
• The energy gap is called Δo (also “10 Dq”), the crystal field
splitting energy.
• The size of Δo depends on ligand strength and metal ion.
(z2, x2–y2)
High Spin eg
0.6∆o
10Dq = ∆o
Low Spin
– or –
0.4∆o
(xy, xz, yz)
3d 3d 3d t2g 3d
Fe3+ Fe3+ Fe3+ Fe3+
Crystal Field Stabilization Energy (CFSE) is the energy difference for

the given electron configuration in the crystal field compared to the
spherical (isotropic) field:
 0.4  # e 0.6
CFSE  # et2 g O eg O 
Calculating CFSE
CFSE is the energy difference for the given electron configuration in
the crystal field compared to the spherical (isotropic) field:
 0.4  # e 0.6
CFSE  # et2 g O eg O 
High Spin Low Spin
Seems like low
(z2, x2–y2) spin should
eg always win! It
would, except
that it costs
energy to pair two
electrons in a
(xy, xz, yz) single orbital
3d t2g 3d (Πtotal see 2.2.3)
Fe3+ Fe3+
CFSE HS   30.4 O   2 0.6 O  CFSE LS   5 0.4 O   0 0.6 O 

0  2 O

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Coordination Chemistry II:

Theories of Electronic Structure

Friday, November 20, 2015

• Magnetic moment – coordination complexes often have unpaired electrons, which

• Electronic spectra – UV-Vis spectroscopy probes electronic transitions between

• Coordination number and geometry – in coordination complexes the observed

• Crystal Field Theory – an electrostatic approach to understanding the electronic

Metal complexes are often brilliantly colored and/or paramagnetic.

Co(NO3)2 K2CrO4 CuSO4

• Crystal Field Theory (simple electrostatic model)

• The transition elements are those elements with partially

Color arises from electronic transitions involving d-orbitals.

Metals with totally empty/full d-orbitals are colorless.

Transition metals with partially filled d-orbitals have color.

Simple electrostatic theory to explain the color and magnetism

400 500 600 800

Many gemstones owe their color to transition metal ions

Corundum (Al2O3): Colorless

CFT was originally developed to explain the colors of these crystals.

• Basic idea: ligands act as point negative charges, and the

The five d-orbitals will split in the crystal field.

i) Separated metal and i

ii) Coordinated metal

The degeneracy of the

energy (including electron- t2g

dxy dxz dyz dz2 dx 2- y2 Δo

• The Barycenter is the average energy of the d-orbitals.

Fe3+ Fe3+ Fe3+ Fe3+

Crystal Field Stabilization Energy (CFSE) is the energy difference for

CFSE HS   30.4 O   2 0.6 O  CFSE LS   5 0.4 O   0 0.6 O 

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