CEM3005W

Inorganic Bonding
Professor Greg Smith

12 lectures

1 Tutorial

Office: 7.08 (Level 7, PD Hahn)

Lab: Synthetic Chemistry Laboratories
Tel: 021-650 5279
Email: Gregory.Smith@uct.ac.za
 Recommended Reading:
Inorganic Bonding

▪ Prescribed Text:
– C. E. Housecroft and A. G. Sharpe, Inorganic Chemistry (Pearson,
3rd ed., 2008; 4th ed., 2012; 5th ed., 2018).
Excellent general-purpose text which covers (in detail) most of the
3rd-year course.

▪ Recommended Texts:
– G.L. Miessler, P.J. Fischer and D.A. Tarr, Inorganic Chemistry
(Prentice Hall, 5th ed., 2014).
– D. F. Shriver and P. W. Atkins, Inorganic Chemistry (OUP, 3rd
ed.,1999).
 From the 2nd Year (CEM2005W)
• Revise lectures on “Introduction to Coordination Chemistry of
the Transition Metals”.

Bond
strengths

Chirality
 Inorganic Chemistry
Bonding in Coordination Complexes
• Introduction - d-block ions
- Lewis acids/bases and dative bonds
- common ligands
- common geometries of complexes
- HSAB
- d-orbitals
• UV-visible spectra and magnetic properties
• Crystal field theory - octahedral complexes
- crystal field stabilisation E
- tetragonal, square planar and Td
- strengths and limitations
• MO theory - introduction
- ligand group orbitals
- Oh complexes,  bonding only
- Oh complexes with -bonding
 1. Introduction 1.1 d-Block ions

1.1.1 Electron configurations

1 2 3 4 5 6 7 8 9 10 11 12
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg

1st row d-block elements valence electron configuration:

4s23dx-2, x = group number, except Cr and Cu
Cr – 4s13d5, Cu – 4s13d10
But ions are ALL 3dx–z, z = charge
2nd and 3rd row atoms more complicated, but ions are the
same.
 Number of d electrons = group number – charge

Exercise
Write down the number of d electrons for the following
ions: V3+, Cr3+, Mn2+, Fe2+, Fe3+, Cu+, Sc3+, Pt2+

1.1.2 Trends in Ionization Energy and Ionic Radius

Ionization energy increases from Sc – Zn

Atomic size decreases from Sc – Ni, but changes are small

and Cu and Zn are slightly larger
Ionic radii:

V2+ > Cr2+> Mn2+ > Fe2+ > Co2+ > Ni2+ < Cu2+ < Zn2+

Sc3+ > Ti3+ > V3+ > Cr3+ > Mn3+  Fe3+ > Co3+ > Ni3+

M2+ > M3+

Changes in ionic size are small across the d-block

Ionic size differs mainly with the charge on the ion and with
magnetic properties (spin state).
1.1.3 Multiple Oxidation States

Sc Ti V Cr Mn Fe Co Ni Cu Zn
0 0 0 0 0 0 0 [0]
1 1 1 1 1 1 1 1 [1]
2 2 2 2 2 2 2 2 2
3 3 3 3 3 3 3 3 3
4 4 4 4 4 4 4 [4]
5 5 5
6 6 6
7
Common oxidation states:
Loss of all d electrons common for first 5 elements, does
not occur for the last 5 – range from M3+ to M7+

Ions in which only partial loss of d electrons occurs is

common, as follows:

M2+ common for all elements from Cr2+ to Zn2+

M3+ common for four elements V3+, Cr3+, Fe3+ and Co3+

The only other common ions are V4+ and Cu+

Other oxidation states usually either require unusual

conditions to form, or stabilizing ligands.
1.2 Acid-base chemistry: Brønsted and Lewis acids and bases

Brønsted-Lowry:
Base: an H+ acceptor
Acid: an H+ donor
Lewis:
Base: an electron pair donor
Acid: an electron pair acceptor

Since H+ has no electrons, it can only bond to an atom with

lone pairs.

All Brønsted bases are Lewis bases

 :

:
E.g. H2O: + H+ → H3O+

:
: :
HO:− + H+ → H2O:

:NH3 + H+ → NH4+

Notice that H+ accepts a pair of electrons in each case

H+ is a Lewis acid

Electron-deficient atoms in molecules, e.g. Be in BeCl2, B in

BF3 are also Lewis acids. They can react with Lewis bases by
forming dative bonds.

E.g. BF3 + :NH3 → H3N-BF3 (usually written H3N→BF3)

All metal ions are Lewis acids.

They can form bonds with donor atoms on ligands (Lewis

bases) that range from ionic to polar covalent

Metal complex formation is a Lewis acid-base reaction.

Brønsted bases are ligands. Their metal binding affinity in

water decreases as pH is lowered owing to competition
with H+.
Not all Lewis bases are significant Brønsted bases.
E.g. Cl−, Br−, I− and CO are not protonated in water even
at pH 0, but are significant Lewis bases, forming
complexes with metal ions.
Molecules or ions with no lone pairs cannot act as ligands.

So, C atoms in organic molecules are not ligands unless

deprotonated
E.g. CH4 is not a ligand, but :CH3− is. Owing to the very high
pKa of organic molecules, C is not a significant ligand in
aqueous solution.
Exceptions are :CN− and :CO which do form metal complexes
in water.
1.3 Common Ligands
In aqueous coordination chemistry the most commonly
encountered donor atoms are O, N, S and halide ions.

There are very many ligand molecules that contain O, N

and S.
 Some are commonly encountered ligands:
Bonding through one donor atom (monodentate)
oxygen donor nitrogen donor halogen donor
atoms atoms atoms
O H N H F−
H H H fluoride
water ammonia
Cl−
-
H O chloride
hydroxide
Br−
N bromide
pyridine (py)
I−
O -
tetrahydrofuran (THF) N C S iodide
thiocyanate
S
O sulfur donor atoms
S -
dimethylsulfoxide (DMSO) O N C S
 Bonding through two donor atoms (bidentate)
oxygen donor nitrogen donor
atoms atoms
O O
H2 N N H2

1,2-ethanediamine or ethylenediamine (en)

- -
O O
oxalate (ox)
N N
2,2’-bipyridine (bpy or bipy)
-

O O

acetylacetonate (acac)
N N

1,10-phenanthroline (phen)
 Bonding through multiple donor atoms (multidentate)
tridentate
NH
NH HN
NH2 NH2
1,4,7-triazaheptane
or diethylenetriamine (dien) NH HN

tetradentate 14-ane-N-4 or cyclam

NH NH
hexadentate
O
NH2 H2 N O
-
1,4,7,10-tetraazadecane O N
-
or triethylenetetramine (trien) N O

O
-
O O
-
O
ethylenediaminetetraacetate
(EDTA4−)
Open chain bidentate and multidentate ligands: chelators or
chelating agents. Complexes are chelates.
e.g. ox, en, dien, trien, EDTA etc.
Cyclic multidentate ligands: macrocycles
e.g. cyclam

1.4 Common Geometries of Coordination Complexes

1st row d-block elements: octahedral, tetragonal,

tetrahedral and square planar complexes are common.
Linear geometry is encountered with Cu(I).
 Stereochemistry of Coordination
Compounds

• Spatial arrangement of ligands around the metal atom / ion

• Arrangement will be such to minimise repulsions

• Coordination Number = 2
– Not a common coordination number
– Occurs for Au(I), Ag(I) and also Cu(I)
– Linear arrangement
– Hybridisation: sp or sdz2

• Coordination Number = 3
– Very rare
– Spatial arrangement is trigonal planar or
can also be trigonal pyramidal

22
 Stereochemistry of Coordination
Compounds
• Coordination Number = 4
– Two stereochemistries possible:
i) Tetrahedral geometry ii) Square Planar

• Coordination Number = 5
– Not as common as CN 4 or 6
i) Trigonal bipyramid ii) Square Pyramid

23
 Stereochemistry of Coordination
Compounds

• Coordination Number = 6
– Most common stereochemistry is octahedral

24
Most are octahedral.

Steric factors mainly explain this – maximizes number of

ligands given the size of the metal ions

[Fe(CN)6]3− [Cr(acac)3] [Co(en)2Cl2]

octahedral pseudo-octahedral
With larger ligands such as halide ions and smaller metal
ions (e.g. Ni(II), Zn(II), d0 ions such as V5+, Cr6+, Mn7+ etc)
tetrahedral coordination occurs

[Cr2O7]2−

[Mn(NtBu)3(O2CMe)]
Tetragonal and square planar geometries occur for
electronic reasons. Tetragonal for d4 high spin, d7 low spin
and d9 ions. Square planar for d8 ions.

[Mn(N3)(acac)2] [Pt(NH3)2Cl2]

tetragonal square planar

d4 d8
1.5 Hard/Soft Acid/Base (HSAB) Theory

What factors are responsible for stability?

Why are some complexes more stable than others?
Why are different oxidation states favoured with different
ligands?

The answers to these questions can be rationalised in three

ways:

▪ Hard / soft acid and base theory (HSAB principle)

▪ Irving-Williams Series
▪ Crystal Field Stabilisation Energy (CFSE) Effects
HSAB Principle
A qualitative way of understanding or predicting stabilities of
complexes e.g., log K1 values for M(II) halide complexes

K1
M2+ + X− MX+

log K1
M/X F– Cl– Br– I–
Zn2+ 0.8 -0.2 -0.6 -1.3
Hg2+ 1.0 6.7 8.9 12.9
Fe3+ 6.0 1.4 0.5 –
Pb2+ 0.3 1.0 1.2 1.3
Ligands with O- and N-donor atoms form stable
complexes with light s- & p-block metal cations, early
d-block metal cations and f-block metal ions.

Ligands with S- and P-donor atoms form more stable

complexes with later d-block metal ions and heavier p-
block metal ions.

Pearson classified cations (Lewis acids) and ligands

(Lewis bases) as either ‘hard’ or ‘soft’

He then used the principle of hard and soft acids and bases
(HSAB) to rationalise these observed patterns in complex
stability.
HSAB Principle
Hard acids (hard metal cations) form more stable
complexes with hard bases (hard ligands), while soft acids
(soft metal cations) show a preference for soft bases (soft
ligands).

Hard metal ions are small, highly charged and not

polarizable.
e.g. Sc3+, Fe3+, Cr3+, Ti4+, Mo5+, Cr6+

Hard ligands have donor atoms that are small,

electronegative, not polarisable and difficult to oxidise.
e.g. NH3, H2O, OH–, OR–, F–, Cl–, NO3–, SO42–
Hard Metal Ions prefer to bond to Hard Ligands

Hard-hard interactions are principally ionic

or electrostatic.
Soft metals ions are large, have relatively low charge and
polarizable.
e.g. All M(0), Cu+, Ag+, Au+, Hg+, Hg2+, Cd2+

Soft ligands are large, less electronegative, polarizable.

e.g. H–, CN–, CO, PR3, I–, RS–, SR2

Soft Metal Ions prefer to bond to Soft Ligands

Soft-soft interactions are principally covalent
 Can also get intermediate behaviour called borderline
e.g. Metal ions: Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Ru3+, Rh3+

e.g. Ligands: Br–, pyridine, N3–

A mismatch between hard and soft components means that

neither ionic nor covalent bonds is optimized.

In extreme cases, redox chemistry can result.

Fe3+ + I– Fe2+ + ½ I2

polarising + polarisable electron transfer

34
35
Exercise
Predict the following:

a) Is AgF(s) or AgI(s) more soluble in H2O?

b) Predict whether thiocyanate (SCN−) will bond to the
following metal ions through S or N: Hg2+, Zn2+, Pt2+.
c) Will Fe3+ react more favourably with OH− or NH3? With
O2− or S2−?
Irving-Williams stability series
Describes trend in stability
constants of the first-row
transition metal M(II) ions.

Stability increased across the

period until Cu(II), then
decreases in Zn(II)
The trend is much more
pronounced for soft bases.

Arises from a combination of

HSAB and crystal field
stabilisation energy.
 1.6 d-Orbitals
Three d orbitals are orientated between the x and y, x and z
and y and z axes. These are termed dxy, dxz and dyz.

The remaining two orbitals lie on the axes.

dx2–y2 is related to dxy except that it lies along the x and y axes
We might then expect an orbital related to dxz but lying
along the x and z axes and another related to dyz along the y
and z axes.

This would give us six orbitals, but there are only five,
corresponding to ml = –2, –1, 0, +1, +2!

The solution is to take a linear combination of dz2–x2 and dz2–y2

which is designated d2z2–x2–y2 and which is usually
abbreviated to dz2.
2. Spectroscopic and Magnetic Properties
2.1 Spectroscopic Properties of d-Block Complexes
Most d-block complexes are coloured.
sodium nickel(II)
chromate nitrate
potassium hexahydrate zinc sulfate
titanium oxide
ferricyanide heptahydrate

scandium manganese(II) copper(II)

oxide chloride sulfate
vanadyl sulfate tetrahydrate cobalt(II) pentahydrate
dihydrate chloride
hexahydrate
However, all Sc(III), Zn(II) and most Cu(I) complexes are
colourless.

Most colours are of low intensity (  1 – 10 M−1cm−1,

compared to  10 000 – 100 000 M-1cm-1 for many organic
chromophores)

Indicates d – d transitions which are Laporte forbidden

l =  1 (Laporte selection rule)

Questions we need to answer:

• How do these d – d transitions arise?

• Why are Zn(II) and Cu(I) colourless?
• Why is [Mn(OH2)6]2+ so pale (  0.04 M−1cm−1)?
• Why is [CoCl4]2− more intense than most of the others
(  100 M−1cm−1)?
• Why are [MnO4]− and [Cr2O7]2− exceptionally intense
( 1000 M−1cm−1)?
2.2 Magnetic Properties of d-Block Complexes
Many d-block complexes are paramagnetic.
This property is very rare in s and p block compounds.
This paramagnetism arises from unpaired electrons in
partially filled d orbitals.

The no. of unpaired electrons (n) in 1st row d-block elements

can usually be determined from the measured magnetic
moment (eff) using the spin-only formula:

eff = (n(n+2))1/2 (Bohr magnetons, BM)

The magnetic moment is directly related to the magnetic
susceptibility (m) which is related to eff:
eff = 2.828(mT)1/2 (Gaussian units)
m can be measured using several techniques including:

A Gouy balance

A Faraday balance

A SQUID magnetometer

An NMR based method (the Evans method)

 n 0 1 2 3 4 5

eff /BM 0 1.73 2.83 3.87 4.90 5.92

Exercise
At room temp. the magnetic moment observed for
[Cr(en)3]Br2 is 4.75 BM. How many unpaired electrons
does the complex have?
The observed value of eff for [VCl4(MeCN)2] at 293 K is
1.77 BM. Deduce the number of unpaired electrons. Is
this consistent with the oxidation state of V?
Ni(II) is a d8 metal ion 3d

From a simple-minded consideration, we expect Ni(II)

complexes have 2 unpaired electrons. This is true in many
cases (referred to as high spin), e.g. [Ni(NH3)6]2+ However
some are diamagnetic, e.g. [Ni(CN)4]2−. These are termed low
spin.

Similarly, Co(III) ions (d6) have 4 unpaired electrons in

[CoF6]3−, but all other Co(III) complexes are diamagnetic.

Other examples: [Cr(OH2)6]2+ 4 unpaired e−, high spin

[Cr(CN)6]4− 2 unpaired e−, low spin
[Mn(OH2)6]2+ 5 unpaired e−, high spin
[Mn(CN)6]4− 1 unpaired e−, low spin

How can we account for high and low spin complexes?

3. Crystal Field Theory 3.1 Octahedral Complexes
To explain the origin of these colours and magnetic
properties we need to understand what happens to the
energy of the d orbitals when the metal ion is surrounded by
ligand donor atoms.

A simple theory called Crystal Field Theory (CFT) can

account for many properties of these complexes.

This is an electrostatic model which accounts for electron-

electron repulsion when a metal ion is embedded in a crystal
lattice, surrounded by anions.
When a metal cation is embedded in a crystal, the effective
nuclear charge of the cation strongly attracts the anions
(ligands)

However, anions will repel electrons in the d orbitals. Note

however, that this accounts for only about 10% of the overall
energy of the complex

We now consider the effects of electron-electron repulsion on

the energies of the d orbitals in an octahedral complex.

First consider a free d10 metal ion (e.g. Cu(I)) in the gas phase

+
Surround this ion by a sphere of negative charge of the same
magnitude as the 6 ligands (e.g. 6 −) at the same distance.

6-

All 5 d orbitals will be raised in energy by the same amount

owing to repulsion since all are equidistant from the sphere
of negative charge and all hold 2 electrons.
Now consider the effect of condensing the negative charge
into 6 points at the vertices of an octahedron. These lie on
the x, y and z axes.
z
−
6-
− −
− −
x
y
−

There is no change in the net energy.

However, the charge is now concentrated near the dz2 and
dx2–y2 orbitals which lie on these axes. They experience
increased repulsion.

− −
− − − −
− −

Both orbitals are raised in energy by the same amount.

On the other hand, the charge has moved further away from
the dxy, dxz and dyz orbitals which lie between the axes.

− − −
− − −
− − − − −
−
− − −
− − −

These orbitals are each lowered in energy by the same

amount relative to the sphere of charge.
The five d-orbitals in an octahedral field of ligands.

53
Crystal field splitting diagram
The dz2 and dx2–y2 orbitals form a doubly degenerate set,
while the dxy, dxz and dyz form a triply degenerate set.

Doubly degenerate orbitals are given the symmetry label e,

while triply degenerate orbitals are labelled t.

Octahedral (as well as square planar and tetragonal)

complexes are centrosymmetric.
Tetrahedral complexes are not.
In centrosymmetric complexes:
- orbitals with a centre of inversion (s and d) are given a
subscript g (from German, gerade = even).
- those without a centre of inversion (p and f) are given the
subscript u (ungerade = uneven)

The energy levels containing dz2 and dx2–y2 orbitals are

labelled eg, while those containing dxy, dxz and dyz orbitals are
called t2g.

The energy separation between the eg and t2g levels is called

oct or 10Dq.

The overall stabilization of t2g relative to the barycentre (the

energy of the spherical field) is equal to the destabilization of
eg for the d10 metal ion.
 Splitting of d-orbital energies by an
octahedral field of ligands.

 is the splitting energy

• Crystal field theory predicts that the d orbitals in a metal

complex are not degenerate.

• The pattern of splitting of the d orbitals depends on the crystal

field, this being determined by the arrangement and type of 57
ligands.
 The Octahedral Crystal Field

• Repulsion by six ligands in

an octahedral complex splits
the d orbitals on the central
metal into t2g and eg levels.
• In an octahedral field the two
sets of d orbitals are labeled
eg (doubly degenerate level)
and t2g (triply degenerate
level)
• The energy separation
between the sets of orbitals
is O (octahedral crystal field
splitting)

d-orbital splitting diagram 58

Thus, eg is raised by 0.6oct, while t2g is lowered by 0.4oct.

Note when fully occupied by electrons 4  0.6oct = 2.4oct and

6  −0.4oct = −2.4oct so that the net energy change relative to
the spherical field is zero.

The E difference between t2g and eg levels explains the fact that
many complexes are coloured. Visible photons carry the right
energy to excite electrons from t2g to eg levels.

In a d1 or d9 complex, e.g. [Ti(OH2)6]3+ or [Cu(OH2)6]2+ the E of

the visible peak maximum corresponds to oct.
 h eg
t2g
d1

h eg
t2g
d9

For d2 – d8 the evaluation of oct is more complex owing to

electron-electron interactions.
 Colours of transition metal complexes
• If the lower d-orbitals are
occupied and the upper
orbitals are vacant or partly
vacant, an electronic
transition (energy jump) from
the lower level to the higher
may occur.
• This energy jump is termed a
d d transition and it
usually absorbs light in the
visible region of the
electromagnetic spectrum.
• The colour of the complex
will depend on the
magnitude of .

62
The color of [Ti(H2O)6]3+

63
Colours of transition metal complexes
• Since for the absorption of a light photon:

o = E = h = hc/l

• If we can measure the l of light absorbed, we can determine the

E (which corresponds to o).

64
Some overall features of the visible spectra of d block metal
complexes can now be explained:

1. Sc(III), d0, is colourless - no d electrons to excite.

2. Zn(II), d10, is colourless - eg level is filled, electrons cannot

be promoted from t2g to eg.

3. [Mn(OH2)6]2+ is a d5 ion:

Excitation of an electron from t2g to eg requires a spin state

change (ms = +½ to –½ or ms = –½ to +½)

h eg
t2g

Violates the spin selection rule S = 0 - intensity is very low.

The magnitude of oct is determined by the strength of the
crystal field. Two extremes are weak field and strong field.

oct (weak field) < oct (strong field)

Factors governing the magnitude of oct:

• identity of the ligands
• identity and oxidation state of the metal

For ligands an empirical finding is that oct increases along

the following series:
I− < Br− < [NCS]− < Cl− < F− < [OH]− <[ox]2−  H2O <
[NCS]− < NH3 < en < bpy < phen < CN− < CO
The spectrochemical series
 Variations in Crystal Field Splitting
• Ligands which cause only a small degree of crystal field splitting
are termed weak field ligands.
• Ligands which cause a large splitting are called strong field
ligands.
• Common ligands can be arranged in ascending order of crystal
field splitting (determined spectrophotometrically).
• This series is called the SPECTROCHEMICAL SERIES.

Weak Field (small o)

I– < Br– < –SCN < Cl– < NO3– < F– < (O2– ≈ –OH ≈ H2O)
< –NCS < NH3 < bipy < –CN < PR3 < CO
Strong Field (large o)

68
 The Spectrochemical series.
• For a given ligand, the color depends on the oxidation state of the
metal ion.

• For a given metal ion, the color depends on the ligand.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD STRONGER FIELD

SMALLER  LARGER 

LONGER l SHORTER l

69
 Other Factors Affecting Crystal Field
Splitting
− O values increase with an increase in the oxidation state of
the metal ion.
– Smaller ion occurs with a higher oxidation state
– Smaller ion leads to shorter M-L bond distances

− O values for corresponding complexes of metal ions in the

same group and with the same oxidation states increase by 30
– 50% on going from the first row transition metal to the
second row transition metal ion and by the same amount
again from the 2nd row to the 3rd row transition metal ion.
– Better M-L bonding occurs with 4d and 5d orbitals

− O values will vary across any transition metal series.

- The splitting is dependent on the stereochemistry of the

70
complexes
For a given metal ion with a given ligand, oct increases with
increasing oxidation state.

For a given group in the periodic table, oct increases down

the group for a given oxidation state and a given ligand.

The spectrochemical series for metal ions is:

Mn(II) < Ni(II) < Co(II) < Fe(III) < Cr(III) < Co(III) < Ru(III)
< Mo(III) < Rh(III) < Pd(II) < Ir(III) < Pt(IV)
Exercise
The wavelength maximum of [Ti(OH2)6]Cl3 dissolved in water
occurs at 493 nm. What is the value of oct in cm−1 and kJmol-1?
What colour will this solution be?
When K3[TiF6] and K3[Ti(CN)6] are dissolved in water one
gives a blue solution and the other a yellow solution. Which
complexes do these correspond to? Explain your reasoning.
What is eff for these complexes?
 Implications and Magnitude of the
Crystal Field Splitting
[Ti(H2O)6]3+
eg

d1

t2g

• An electron in one of these orbitals is stabilised by an amount of

2/5 O.
• This stabilisation is referred to as the crystal field stabilisation
energy (ligand field stabilisation energy).
• The crystal field stabilisation energy is a measure of the net
energy of occupation of the d orbitals relative to their mean
energy.

For t2gxegy configuration: CFSE = (-0.4x + 0.6y)o 74

 3.2. Crystal Field Stabilization Energy: High and Low Spin
Complexes
Reference to the crystal field splitting diagram allows us to
calculate the crystal field stabilization energy (CFSE)
relative to the barycentre in units of oct
Thus:
eg
+ 0.6oct
d1 CFSE = −0.4oct
t2g - 0.4oct

eg
+ 0.6oct
d2 CFSE = 2  −0.4oct = −0.8oct
t2g - 0.4oct

eg
+ 0.6oct
d3 CFSE = 3  −0.4oct = −1.2oct
t2g - 0.4oct
 d1 (Ti3+) d2 (V3+) d? (Cr3+)
eg eg eg

t2g t2g
t2g
CFSE = -2/5O CFSE = -4/5O CFSE = ?O
[Ti(H2O)6]3+ [V(H2O)6]3+ [Cr(H2O)6]3+

d? (Mn3+) d? (Fe3+)
eg eg

t2g t2g

CFSE = ?O CFSE = ???

76
[Mn(H2O)6]3+ [Fe(H2O)6]3+
When we reach d4 two arrangements are possible:
eg eg
d4 or
t2g t2g

low spin high spin

The low spin case would seem favourable: the 4th electron
occupies the lower energy level - t2g.
But, spin pairing involves loss of exchange energy and
electrostatic repulsion. There is a positive spin-pairing
energy P.
The magnetic properties of d-block metal complexes are now
explained.
If oct < P, then the complex is high spin, and if
oct > P, it is low spin.
For the high spin complex
CFSE = 3  −0.4oct + 0.6oct = −0.6oct
For the low spin complex
CFSE = 4  −0.4oct + P = −1.6oct + P
High and low spin states also occur for octahedral complexes
of d5, d6 and d7 ions.
eg eg Note that d-d
d5 or transitions are only
t2g t2g spin forbidden for
high spin the high spin case
low spin

eg eg
d6 or
t2g t2g

low spin high spin

 eg eg
d7 or
t2g t2g

low spin high spin

In general, for the high spin case:

CFSE = nt2g  −0.4oct + neg  0.6oct

For the low spin case:

CFSE = nt2g  −0.4oct + neg  0.6oct + (npaired)  P

For d8, d9 and d10 ions, only one arrangement is possible

and CFSE = nt2g  −0.4oct + neg  0.6oct
 eg
d8
t2g

eg
d9
t2g

eg
d10
t2g
High or low spin state is thus determined by the crystal
field strength.

For a given metal ion in a given oxidation state:

- low spin complexes are more likely with ligands high in

the spectrochemical series (e.g. CN−, CO).

- high spin complexes are more likely with ligands low in

the spectrochemical series (e.g. halides, OH−).

However, this is metal dependent:

e.g. nearly all Mn(II) complexes are high spin, one of the
only common low spin complexes is [Mn(CN)6]4−
All Co(III) complexes are low spin except [CoF6]3−
 Weak and Strong Crystal Fields
eg eg eg
d1 d2 d3

t2g t2g t2g

eg
4
d
eg d4
HIGH SPIN LOW SPIN
Weak field Strong field
Spin-free Spin-paired
t2g
t2g

Ligands with strong interactions to the metal are called strong field ligands.
85
Ligands with small interactions with the metal are called weak-field ligands.
The effect of ligand on splitting energy.

86
High-spin and low-spin complex ions of Mn2+.

88
Orbital occupancy for high- and low-spin complexes
of d4 through d7 metal ions.

high spin: low spin: high spin: low spin:

weak-field strong-field weak-field strong-field
ligand ligand ligand ligand

89
 Problem-Solving in Coordination
Chemistry
The following order is observed in the
spectrochemical series for the ligands listed,

I– < Br– < –SCN < Cl– < NO3– < F– < (O2– ≈ –OH ≈ H2O)
< –NCS < NH3 < bipy < –CN < PR3 < CO
It was observed that for the two 6-coordinate
cobalt complexes, [CoF6]3- and [Co(NH3)6]3+, one
is diamagnetic and one is paramagnetic. How
many unpaired electrons are there in the
paramagnetic complex ion?
91
• The magnetic moment of the complex
[Mn(NCS)6]4- is found to be 6.06 B.
What is its electron configuration?

93
 Exercise

K[MnCl3(OH2)3] is very pale pink with a measured eff =

5.89 BM at 298 K. On the other hand, K4[Mn(CN)6] is dark
blue with eff = 1.75 BM at 298K. Calculate the CFSE for
each of these complexes and explain your reasoning.

3.3. Crystal Field Theory for Tetragonal, Square Planar and

Tetrahedral Complexes
CFT can be successfully applied to non-octahedral complexes

3.3.1 Tetragonal Complexes: Jahn-Teller Distortion

In the cases of d4 high spin, d7 low spin and d9, an uneven

number of electrons occupy the eg orbitals
 Jahn-Teller Effect

• Consider Cu2+ (by far the most common example)

eg*

t2g

• There are two ways of arranging the eg* electrons (which are
antibonding and not pure d, but the result is the same)
– (dz2)2(dx2-y2)1 - leads to more antibonding character on the z
axis and hence elongation of bonds in that direction
– (dz2)1(dx2-y2)2 - leads to more antibonding character in the xy
plane and hence elongation of bonds in that direction
96
 eg eg eg

t2g t2g t2g

high spin low spin

d4 d7 d9

They undergo tetragonal distortion to remove degeneracy of

the eg orbitals. This is called Jahn-Teller distortion.

e.g. In a d4 complex, if the electron occupies dz2, it repels the

axial ligands. Elongation of axial bonds relieves repulsion
and lowers the energy of the dz2 orbital.

If dx2–y2 is occupied the equatorial bond lengths elongate and

this d orbital is lowered in energy.
 Jahn-Teller Effect

dx2-y2

dz2
distortion

dxy
dxz, dyz

– Net gain in CFSE (2e– lowered and raised in energy)

– Degeneracy of eg* is lifted (state becomes single degenerate)

98
 L
n+
L n+
a L
a L
L L
M e a>e M e a<e
L L
L L
L

The first case is much more common.

Unequal occupancy of the t2g set usually cause negligible

distortion since the dxy, dxz and dyz orbitals do not point directly
at the ligands.

Examples of tetragonal complexes exhibiting Jahn-Teller

distortion are [Cr(OH2)6]2+, [NiF6]3− and [Cu(OH2)6]2+.
 Jahn-Teller Effect
Definition: Any non-linear molecule in a degenerate electronic
state will distort so as to remove that degeneracy

• For a tetrahedral metal ion in the ground state, expect Jahn-

Teller distortion for d3, d4, d8 and d9
…. but this is rarely observed as distortions are very small
• For octahedral metal ion in the ground state, expect Jahn-Teller
distortion for d1, d2, d4 (HS or LS), d5 (LS), d6 (HS), d7 (HS or
LS) and d9
…. but effects from uneven occupancy of t2g are small and rarely seen
– Effects are most obvious when the eg* level is unevenly occupied
101
• i.e. HS d4, LS d7 and d9
 3.3.2 Square Planar Complexes
Electronic factors are also responsible for the formation of
square planar complexes by d8 metal ions such as Ni(II),
Pd(II), Pt(II) and Au(III) which are diamagnetic (low spin).
In an octahedral field 2 electrons occupy the high energy eg
level.
Removal of the axial ligands drastically lowers the energy of
the dz2 orbital which can now be occupied by both electrons.
The net CFSE is then lower in a strong crystal field where the
lowering of the energy of the dz2 orbital > P
Square planar complexes: Ni(II) with strong field ligands
(e.g. [Ni(CN)4]2−), all complexes of the heavier metal d8 ions
Pd(II), Pt(II) and Au(III).
The crystal field splitting diagram of tetragonal and square
planar complexes is readily derived from the octahedral case.
 Square Planar Complexes
d(x2–y2) d(x2–y2)

d(z2) d(z2)
d(xy)
d(xy)
d(xz), d(yz)
d(xz), d(yz)

Square planar
Regular octahedron
Axial elongation
Best way of optimising CFSE for d8 configuration (sq. pl. d8 has
higher CFSE than octahedral d8 - octahedral is higher for all other
104
configurations)
 Square Planar Complexes
• Why does square planar geometry not always occur for d8?

– CFSE is only a small part of the overall energy.

• It is thermodynamically more favourable to form 6 bonds
rather than 4; this will of course be disfavoured
entropically.
• CFSE often tilts the balance in favour of square planar

– With 4 ligands, square planar geometry is sterically less

favourable than tetrahedral geometry.

105
 Square Planar Complexes
• Small, strong field ligands favour square planar
• Large, weak field ligands will favour tetrahedral
– e.g. [NiCl4]2– tet. [Ni(CN)4]2– sq. pl.
NiCl2(PPh3)2 tet. Ni(NCS)2(PPh3)2 sq. pl.
– Pd(II) and Pt(II) are essentially always square planar
{larger CFSE and reduced steric effects (longer M–L
bonds) for 2nd/3rd row transition metals}
– Also Au(III), Rh(I) and Ir(I) are also d8 and often form
square planar complexes, e.g. [AuF4]– , [RhCl(PPh3)3]

106
 Square Planar Complexes
– For Co(I), Rh(I) and Ir(I), d8 configuration is realised in
the +1 oxidation state; d8 configuration prefers square
planar geometry but the +1 oxidation state does not
accentuate this preference (low CFSE)

– Most Co(I) species are 5-coordinate

– Rh(I) and Ir(I) are often square planar with  acceptor

ligands but will readily expand their coordination sphere.

107
 Square Planar Complexes
• Planar/octahedral equilibria
– The thermodynamic preference for square planar or
octahedral geometry can be finely balanced
– Dissolving planar Ni(II) complexes in a good donor
solvent (H2O, pyridine etc.) can give octahedral
complexes
S
L L L L Mixture of the two
Ni + 2S Ni forms can give
L L L L
S
anomalous magnetic
Square planar behaviour in solution
diamagnetic octahedral
paramagnetic

e.g. Lifschitz salts: [Ni(L–L)2]X2 (sq. pl)

or [Ni(L–L)2X2] (oct.) 108
where L–L = en derivative, X = variety of anions
 Square Planar Complexes
• Planar/tetrahedral equilibria
– If steric and electronic factors are finely balanced, the
metal may not express a great preference for square planar
over tetrahedral geometry or vice versa
• e.g.
PEtPh2
Br PEtPh2
Ni
Ph2EtP Br Ni
Br
PEtPh2
Square planar Br
brown
diamagnetic Tetrahedral
Green
paramagnetic ( = 3.20 BM)
• Can get a mixture with anomalous magnetic behaviour
109
 3.3.3 Tetrahedral Complexes
In a tetrahedral complex none of the d orbitals point
directly at the ligands, but dxy, dxz and dyz are closer than dz2
and dx2–y2.

Note: orbitals lying on the axes are half a face (diagonal) from
the ligands, while the dxy, dxz and dyz orbitals are only half an
edge away.
The crystal field splitting diagram looks like the inverse of
the octahedral case, but tet is smaller than oct.
Note: energy levels are called t2 and e. A tetrahedron is not
centrosymmetric, therefore no subscript g. The t2 > e.

Since tet is only 4/9oct, tet is always < P, even for strong
fields and all tetrahedral complexes are high spin.

Examples of tetrahedral complexes: [CoCl4]2− and

[NiCl4]2−.
The lack of a centre of symmetry relaxes the Laporte rule
and so tetrahedral complexes have more intense spectra
(typically   10 – 100 M-1cm-1)

CFSE = ne  −0.6tet + nt2  0.4tet

= ne  −0.27oct + nt2  0.18oct
 Exercise
Ni(py)4(ClO4)2 exists in two forms. A blue paramagnetic
form and a yellow diamagnetic form. How can this be
explained? [Note: ClO4− is a weak ligand]

3.4. Strengths and Limitations of Crystal Field Theory and

Ligand Field Theory
3.4.1 Ligand Field Theory

Ligand field theory (LFT): an extension of CFT which uses

parameters derived from spectroscopy (oct and Racah
parameters that relate to electron-electron repulsion), rather
than treating ligands as fixed-point charges.

For qualitative descriptions of the type we have looked at,

LFT and CFT give identical results and LFSE = CFSE
3.4.2 Rationalization of Thermodynamic Trends
CFT and LFT can explain certain thermodynamic trends.
• lattice energies of salts of d-block metal ions
• hydration energies of d-block metal ions
• formation of inverse spinels

Lattice energy and hydration energy trends follow a pattern

virtually identical to the LFSE/CFSE.

maxima occur at d3 and d8 for high spin metal ions.

minima at d0, d5 and d10

The large background E shows that LFSE/CFSE makes a

small contribution to overall energy which increases steadily
across the period.
Spinel: MgAl2O4.
Complex structure - a cubic close packed array of O2− ions,
1/ of the T holes are occupied by Mg2+ ions and ½ the O
8 d h
3+
holes are occupied by Al ions.

A number of other minerals, including chromite (FeCr2O4)

have the same structure (some also form with M4+ and M2+
ions).
This structure usually most stable, because the M3+ ion is
surrounded by more anions in the Oh hole which is
electrostatically favoured.
 ½ occupancy
1 site in the cell
1/ occupancy
8 x
x x
x
x x
x x
x
x
x x
x
Shared between 4 cells
1/
8  8 + ½  6 = 1 + 3 = 4 spheres per unit cell
1 + ¼  12 = 1 + 3 = 4 octahedral sites
 1 octahedral site per sphere
 3 octahedral holes

6 tetrahedral holes

 2 tetrahedral holes per octahedral hole

Some d-block metal ions form inverse spinels where M2+ ions
occupy Oh holes and ½ the M3+ ions occupy Td holes.
e.g. Ni2+Ga3+2O4, Co2+Fe3+2O4 and Fe2+Fe3+2O4.
Ga3+ and Fe3+ have 0 CFSE, while Fe2+, Co2+ and especially Ni2+
have significant CFSE.
Since oct > tet these 2+ ions preferentially occupy the
octahedral holes.

In chromite, CFSE Cr3+ > CFSE Fe2+ and a normal spinel is

formed. Similarly, Zn2+Fe3+2O4 forms a normal spinel because
neither ion has any CFSE.

In these examples, E of the lattices is very small and CFSE

differences are sufficient to tip the balance from spinel to
inverse spinel.
Exercise
Is the following mixed metal oxide likely to adopt an inverse
spinel structure? Explain. Ni2+Fe3+2O4
What about Ni2+Cr3+2O4? [Here oct: Ni2+ = 8500 cm-1, Cr3+ =
17 400 cm-1]

3.4.3 Limitations of CFT and LFT

CFT and LFT are unable to explain:

the position of ligands in the spectrochemical series and hence
to account for the magnitude of oct.
The existence of intense absorbance bands in metal complexes
such as [Fe(SCN)6]3−, [Cr2O7]2− and [MnO4]−.

To address this, we must turn to molecular orbital theory

(MOT).
4. Molecular Orbital Theory (MOT)
4.1 Introduction to MOT, a Short Revision
Consider H2+, which consists of two protons and one
electron.
The Schrödinger equation can be solved using the Born-
Oppenheimer approximation. This treats the nuclei as
stationary and then solves the Schrödinger equation for the
electron only.
The resulting wavefunctions are called molecular orbitals
(MOs).
However, the analytical solutions are very complicated and
provide little chemical insight.
A much more useful approach is to approximate MOs by a
linear combination of atomic orbitals (LCAO).
Rules:
Interactions of atomic orbitals (AOs) are allowed if the
symmetries of the AOs are compatible.
Interactions are efficient if there is significant overlap.
Interactions are efficient if the energies of the AOs are
similar.
A fundamental principle: the number of MOs that can be
formed is equal to the number of AOs of the constituent
atoms.
In H2+ the two 1s atomic orbitals can be combined in two ways

In phase: MO = N[1 + 2]

Out of phase: MO = N[1 − 2]
N, the normalization factor ensures that MO2 = 1 over all
space (i.e. the probability of finding the electron somewhere
in space is exactly 1)

The in-phase combination  constructive interference and

results in increased electron density between the nuclei,
lowering the energy relative to separate atoms - a bonding
orbital.

The out of phase solution = destructive interference and

results in a node between the nuclei with zero electron
density. Repulsion of the nuclei causes an increase in energy
- an antibonding orbital.
This can be shown in the form of an MO diagram which can
be filled with electrons similar to AOs for H2 and He.

The bond order is ½(nbonding e – nantibonding e)

For H2 = ½(2 – 0) = 1, corresponding to a single bond

For He = ½(2 – 2) = 0, no bond is formed

The H2 MOs can be represented as follows:

For a heteronuclear diatomic molecule such as HF, the AOs
are not identical in energy. Now AOs on each atom no longer
make equal contributions to the MOs.
The AO closer in energy to the MO makes a larger
contribution.

Overlap between orbitals is not always allowed by symmetry.

Thus in HF, two of the p orbitals lead to non-bonding
interactions with the H 1s orbital.
The third gives rise to a bonding-
antibonding pair.

Orbitals with very

different energies are
also non-bonding,
e.g. F 2s
4.2 Ligand Group Orbitals - Polyatomic Molecules
In a polyatomic molecule, the usual approach is to combine
some of the atoms to form ligand group orbitals. This
simplifies an otherwise complicated problem.
The no. of ligand group orbitals = number of AOs used
An example is H2O
The two H 1s AOs can be taken together as ligand group
orbitals.
When they have the same phase, they can combine with
the O 2s orbital as well as the pz orbital.
When they have opposite phase, they can combine with
the O 2py orbital.
The O 2px orbital is non-bonding.
 4.3 Molecular Orbital Theory for Octahedral
Complexes (With -Bonding Only)
For a d-block metal complex, s, p and d orbitals have
suitable energies for interaction with ligand orbitals (for 1st
row d-block ions 3d, 4s and 4p).

6 ligands give 6 ligand group orbitals by combining in

various ways so as to be able to overlap with metal AOs.

Consider each of the s, p and d orbitals on the metal and

select suitable ligand group orbitals to overlap with metal
AOs

The s, px, py, pz, dz2 and dx2–y2 all have suitable symmetry
to form bonding and antibonding orbitals with the
ligands.
 134
Molecular orbital theory for octahedral complexes
 bonding
• 6 of the metal orbitals are directed along the axes
and are capable of forming σ bonds with the ligands
• Metal s and p orbitals are clearly of the correct
symmetry to overlap with the ligands

z
z z z

y y y y

4s M
4px 4py 4pz

x x x x
 135
Molecular orbital theory for octahedral complexes

 bonding
• Of the metal d orbitals, two are correctly aligned to form
 bonds; the remaining three orbitals will be non-bonding
z z

y y

3d(z2) 3d(x2-y2)

x x

BONDING

x
Using dxy
orbital as y
Overlap integral is zero
an example i.e. NON BONDING
The s orbital forms MOs with a totally symmetrical ligand
group orbital labelled a1g and a1g*

The px, py and pz orbitals form a triply degenerate set of MOs

labelled t1u and t1u*
The dz2 and dx2–y2 orbitals form a doubly degenerate set
labelled eg and eg*
Owing to significant overlap and similar energy of metal and
ligand orbitals, the interaction is efficient in all these
orbitals.

The dxy, dxz and dyz orbitals do not possess the correct
symmetry for overlap, forming a triply degenerate set of
non-bonding orbitals labelled t2g.
 Molecular orbital diagram for ML6 ( bonding only)

a1g*

4p (t1u) t1u*

Antibonding
4s (a1g)
M

eg*

t2g Non Bonding

3d
(t2g + eg) eg t1u a1g
6L

eg

t1u
Bonding

138
a1g
 Molecular orbital diagram for ML6 ( bonding only)
• Now add electrons
• Each ligand will a1g*
donate 2e–, i.e. a
total of 12e– from 4p (t1u) t1u*

all 6 ligands

4s (a1g)
M

eg*

t2g
3d eg t1u a1g
(t2g + eg)
6L

eg

t1u

• Now focus on the fate of the

139
metal electrons a1g
 Molecular orbital theory for octahedral complexes
 Bonding
e g*

t2g

• Any extra electrons from metal d orbitals go into t2g/eg* levels

– Thus, metal d-electrons do not participate in forming M–L -bonds, but
remain in the frontier orbitals
• eg* levels {dx2-y2 and dz2 according to CFT} are actually weakly
antibonding molecular orbitals, not pure metal d-orbitals
• t2g orbitals in contrast are pure d-orbitals (by  bonding only
140
mode
 Molecular orbital theory for octahedral complexes
 Bonding

• Separation of t2g and eg* (i.e. o) depends on extent of

interaction of metal and ligand orbitals
– stronger bonding will lower eg and raise eg*, giving
bigger o

• Consequences of the  bonding model

– Any electron in eg* is antibonding and will weaken
and lengthen bonds in the complex.

141
 Molecular orbital theory for octahedral complexes
 Bonding

• Consequences of the  bonding model

– Occupancy of eg* levels lengthens M–L bonds,
and results in faster substitution reactions.
– Occupation of all bonding and non-bonding
orbitals requires 18 electrons, 12 from ligands
and six from metal (see course on
Organometallic chemistry)

142
Each ligand is an electron pair donor, so the six ligands
supply 12 electrons.

The t1u, a1g and eg orbitals can accommodate 12 electrons.

Notionally these orbitals are always filled with the 12 ligand
electrons.

Occupancy of the t2g and eg* orbitals is then determined by

the number of d electrons on the metal ion which
notionally occupy these orbitals.

Note that the t2g and eg* orbitals in the MO approach can
be compared to the t2g and eg levels in CFT and LFT and
the energy difference between them is oct.
Note: transitions can occur from energy levels with
predominantly ligand character and u symmetry to
predominantly metal t2g or eg* levels.

These are Laporte allowed and account for intense

absorbance exhibited by some metal complexes.
- a ligand to metal charge transfer (LMCT) band.
Transitions from predominantly metal t2g and eg* orbitals
to low lying empty orbitals predominantly on the ligand
can also occur – a metal to ligand charge transfer (MLCT)
band.
The intense colours of [Fe(SCN)6]3−, [Cr2O7]2− and [MnO4]−
arise from LMCT bands.
4.3 Octahedral Complexes With  and -Bonding
Now consider the effect of -bonding on the complex. This
concept has no counterpart in the CFT or LFT approach.

Ligands such as halide ions I−, Br− and Cl− have filled p
orbitals which can interact with dxy, dxz and dyz orbitals side-
on to form -bonds.

Filled orbitals lie relatively low in energy (but higher than

the orbitals involved in -bonding). The result is splitting of
the t2g orbitals into a bonding t2g and anti-bonding t2g* set.
e.g. MCl6n−

oct
18 lone
pair
orbitals
 e.g. MCl6n-

15 filled,
non-
oct bonding
more M t2g*
orbitals on
character L 18 lone
pair
t2g orbitals
filled, more L
character

Mn+ 6L
The three metal d orbitals can form MOs with three filled
ligand group orbitals with a total of 6 electrons.

Notionally, the t2g orbitals are thus filled with ligand

electrons and the metal d electrons occupy the t2g* orbitals.

Note that the antibonding character of t2g* means that

these orbitals are raised in energy closer to the eg* orbital,
hence decreasing oct.

Thus: ligands with more than one lone pair on the donor
atom (e.g. halide ions) can -bond which will reduce oct
relative to ligands with donor atoms containing only one
lone pair (and no ligand * orbitals, e.g. NH3).
Ligands that contain -electron systems such as py, phen,
CN− and CO have empty * antibonding orbitals. These too
can interact with dxy, dxz and dyz orbitals on the metal ion to
form -bonds.

These empty ligand orbitals lie higher in energy than filled

orbitals and contribute no electrons. The effect is to lower
the t2g orbitals relative to eg* and hence increase oct.
e.g. M(CO)6n+

12 empty
C−O *
orbitals
oct
 e.g. M(CO)6n+
9 empty,
non-bonding
empty more orbitals on L
t2g*
L character
12 empty
C−O *
orbitals

oct

more M t2g
character
 Molecular orbital theory for octahedral complexes
 Bonding
•  effects are subdivided into two extreme cases
a1g*

4p (t1u) t1u* The ligand orbitals

are empty and of
relatively high
4s (a1g)
energy - the ligand is
eg*
a  acceptor

t2g
3d
(t2g + eg)
The ligand orbitals
eg t1u a1g are filled and of
eg
relatively low energy
t1u - the ligand is a
 donor
156
a1g
 Molecular orbital theory for octahedral complexes
 Bonding

•  donor ligands
– e.g. Halide anions possess
lone pairs in  orbitals

:
M Cl
eg* eg*
New o
t2g* (and hence the metal
Old o t2g* electrons) are raised in energy –
the orbital is now antibonding
t2g
filled, low energy
ligand  orbitals
Ligand  electrons t2g 157
lowered in energy
Molecular orbital theory for octahedral complexes
 Bonding

•  acceptor ligands
• e.g. CN–, CO (using * orbitals)
• e.g. PPh3 {using d orbitals (or more correctly * orbitals
but the symmetry is the same whichever)}
t2g*

empty, high energy

eg* eg*
ligand  orbitals

Old o
t2g New o
t2g (and hence the metal
electrons) lowered in energy158
t2g
Molecular orbital theory for octahedral complexes
 Bonding

• The metal t2g orbitals cannot participate in  bonds

but are of the correct symmetry to overlap with 
orbitals of ligands (if there are any)

• In contrast, the eg and eg* orbitals cannot participate

in  bonding of ligands

• Three types of  interactions are commonly

encountered

159
 Molecular orbital theory for octahedral complexes
 Bonding
Metal d-orbital

Ligand p-orbital
d()–p() interaction (e.g. halide ligand)

d()–d() interaction Ligand d-orbital

(e.g. P, S, ligand)

Ligand * orbital
d()–p(*) interaction –
(e.g. CN , pyridine, CO...)

160
Molecular orbital theory for octahedral complexes
 Bonding

• For -donors:
– Ligand has filled  orbitals which overlap with the
metal t2g orbitals giving a  bond
– Thus electron density is transferred from the
ligand to the metal
– Complexes are favoured when the central metal
has a high oxidation state and is ‘short of
electrons’
– Ligand  orbitals are lower in energy than the
metal t2g orbitals
– Delocalising  electrons from the ligand to the
metal reduces the value of 
– E.g. Cl-, F-, Br-
161
Molecular orbital theory for octahedral complexes
 Bonding

• For -acceptors:
– Ligands such as CO, CN- and NO+ have empty  orbitals
with the correct symmetry to overlap with metal t2g orbitals,
forming  bonds ➔ back bonding

  orbitals on the ligands are of higher energy than the metal

t2g orbitals

– No more electrons are added as ligand  orbitals are empty,

but the  interaction increases the value of o.

162
Molecular orbital theory for octahedral complexes
 Bonding

•  donor ligands will increase the e– density at a metal

and hence often combine with metals with empty or
poorly filled d orbitals (ie metals in a high-ish oxidation
state)

•  acceptor ligands will decrease the e– density at a

metal and often combine with metals with fully or nearly
full d orbitals (ie metals in a low-ish oxidation state)

163
Molecular orbital theory for octahedral complexes
 Bonding

• Overall:  donor ligands decrease o

•  acceptor ligands increase o

• Similarly: good  donors increase o

• poor  donors decrease o

• We can now explain the spectrochemical series.

164
 Spectrochemical Series

Weak Field (small o)

I– < Br– < –SCN < Cl– < NO3– < F– < (O2– ≈ –OH ≈ H2O)
< –NCS < NH3 < bipy < –CN < PR3 < CO
Strong Field (large o)

• Points to note
• Series approximates to Gp 17 < Gp 16 < Gp 15 < Gp 14
• Strong field ligands are all  acceptors
• NH3 > H2O as it is a better  donor (less electronegative)
• Weak field ligands are  donors

165
Note that we have now explained the outline of the
spectrochemical series:

-donor ligands such as Cl−, Br− and I− lie low in the

spectrochemical series relative to -only ligands such as
NH3, while -acceptor ligands such as CN− and CO lie high
in the spectrochemical series.

The -donor ligands result in small oct values and are thus
more likely to give high spin complexes, while -acceptor
ligands give rise to large values of oct and are more likely to
lead to low spin complexes.
Note: -donor ligands supply 18 electrons which notionally
occupy the t1u, a1g, eg and t2g orbitals.

The metal d electrons notionally occupy the antibonding t2g*

and eg* orbitals. This tends to stabilize high oxidation state
complexes.

However, the gap between bonding and antibonding orbitals

in high oxidation state complexes typical in aqueous
coordination chemistry is small.

So occupancy of the t2g* and eg* levels by a few electrons is

not greatly destabilising.
-acceptor ligands supply 12 electrons which notionally
occupy t1u, a1g and eg.

Up to 6 metal d electrons can notionally occupy the t2g

bonding orbitals and the rest go into the eg* antibonding
orbitals, which is much more strongly antibonding
because of the large oct.

Thus octahedral complexes with d7, d8 and d9 electron

configuration are disfavoured by such ligands (e.g. CO).

This gives rise to the 18-electron rule which is

important in low oxidation state metal complexes with
-acceptor ligands typical in organometallic chemistry.