Coordination Chemistry II

Bonding, including Crystal Field Theory

and Ligand Field Theory

Many of the figures are copied from Internet or class notes or scan copy of
books from others
CYL101
IIT Ropar

Why Study Chemistry of Transition Metals

 Transition metals are found in nature

 Rocks and minerals contain transition metals
 The color of many gemstones is due to the presence of
transition metal ions
 Rubies are red due to Cr
 Sapphires are blue due to presence of Fe and Ti
 Many biomolecules contain transition metals that are
involved in the functions of these biomolecules
 Vitamin B12 contains Co
 Hemoglobin, myoglobin, and cytochrome C contain Fe

1
 Why Study Chemistry of Transition Metals

 Transition metals and their compounds have many useful

applications
 Fe is used to make steel and stainless steel
 Ti is used to make lightweight alloys
 Transition metal compounds are used as pigments
 TiO2 = white
 PbCrO4 = yellow
 Fe4[Fe(CN)6]3 (prussian blue)= blue
 Transition metal compounds are used in many industrial processes

sapphire Emeralds

2
 Introduction

Emerauld: chromium (III) into crystalline

Be3Al2Si6O18

Amethyst: iron (II), iron (III), titanium

(IV) in Al2O3

Ruby: chromium (III) in Al2O3

Coordination Complexes in Living Systems

Porphyrines, hemoglobin

Vitamin B12

3
 Chlorophyll: A very important porphyrine that converts
solar photons into food energy

Chlorophyll (C55H72N4O5Mg)

Bonding Approaches

EAN Rule: non-metal follows 8e and

Coordination complexes follows 18e.
e.g. K[Fe(CN)6] or [Co(NH3)6]Cl3

 Valence Bond theory provides the hybridization for

octahedral complexes. For the first row transition metals,
the hybridization can be: d2sp3 (using the 3d, 4s and 4p
orbitals), or sp3d2 (using the 4s, 4p and 4d orbitals).

4
 Valance Bond Model
Co3+ ion (d6)
3d 4s 4p 4d

3d 4s 4p 4d

sp3d2
• Outer 4d orbital is used so called Outer orbital complex: the energy of
4d is very high so these complexes are reactive or labile. The magnetic
moment depends on number of unpaired electron are
3d 4s 4p 4d

3d 4s 4p 4d

d2sp3

Inner orbital complex: Since 3d is used; so more stable and Low spin

Valance Bond Model

Ligand = Lewis base
Metal = Lewis acid
s, p and d orbitals give hybrid orbitals with specific geometries
Number and type of M-L hybrid orbitals determines geometry of the complex

Octahedral Complex
e.g. [Cr(NH3)6]3+

5
4 coordinated complexes

Tetrahedral
e.g. [Zn(OH)4]2-

Square Planar
e.g. [Ni(CN)4]2-

Limitations of VB theory
• Cannot account for colour of complexes
• May predict magnetism wrongly
• Cannot account for spectrochemical series

Crystal Field Theory

400 500 600 800

The relationship
between colors
and complex
metal ions

6
 Crystal Field Theory (CFT)
(Text : JD Lee; pp.204-222)
• CFT largely replaced VB Theory for interpreting the chemistry of
coordination compounds.
• It was proposed by the physicist Hans Bethe in 1929.
• Subsequent modifications were proposed by J. H. Van Vleck in
1935 to allow for some covalency in the interactions. These
modifications are often referred to as Ligand Field Theory.
• For a review on the evolution of bonding models see:
C. J. Ballhausen, J. Chem. Ed. 1979 56 194-197, 215-218, 357-361.

In crystal field theory, the electron pairs on the ligands

are viewed as point negative charges that interact with
the d orbitals on the central metal. The nature of the ligand
and the tendency toward covalent bonding is ignored.

d Orbitals

7
d-orbitals: look attentively along the axis
Linear combination of
dz2-dx2 and dz2-dy2

d2z2-x2-y2

Octahedral Field

8
 Crystal Field Theory
Ligands, viewed as point charges, at the corners of an octahedron
affect the various d orbitals differently.

9
 Crystal Field Theory

Octahedral Field
Octahedral Field
•If ratherthan
•If rather
with the metal,
than
a spherical Octahedral Field
a spherical
field,field,
the degeneracy
discrete
discrete
of
point charges
point charges
the d orbitals isthe
(ligands)(ligands)
removed
are allowed
(or, better
are to allowed
interact to
said, lifted). The
interact with the metal, the degeneracy of d orbitals is removed (or,
•If rather than a spherical field, discrete point charges (ligands) are allowed to interact better
splitting of d orbital energies and its consequences are at the heart of crystal field theory.
said, lifted).
with the The
metal,splitting of d of
the degeneracy orbital energies
the d orbitals and its(or,consequences
is removed are
better said, lifted). at the
The
splitting of d orbital energies and its consequences are at the heart of crystal field theory.
heart of crystal field theory.
eg
eg

E
E

Mn+ t
t2g2g
Mn+

• •Not
Notallall
d orbitals
•Not will interact
dallorbitals
d orbitals to the
will interact
will interact tosame
to the extent
same
the with
extent
same the
with
extent thesix
sixpoint
with point charges located
charges located
the six point charges
on the on
+x,the
-x,+x,
+y,-x,
-y,+y,
+z-y,
and+z -z
and -z axes
axes respectively.
respectively.
located on the +x, -x, +y, -y, +z and -z axes respectively.
•The orbitals which lie along these axes (i.e.2 x22-y2,2 z2) will be destabilized more that
• •The
Theorbitals
orbitals which lie along these axes (i.e. x -y , z ) 2will2 be2 destabilized more that
which lie
the orbitals along these axes(i.e.
(i.e. xxz,-yyz)., z ) will be destabilized
26
26
the orbitals whichwhich lie in-between
lie in-between the the
axesaxes
(i.e. xy,xy,
xz, yz).
more that the orbitals which lie in-between the axes (i.e. xy, xz, yz).

10
 Octahedral complexes

Octahedral Complexes
The repulsion
Octahedral between ligand
Complexes
lone pairs and the d orbitals on
the metal results in a splitting of
the energy of the d orbitals.

27 27

d Orbital Splitting
 The gap in these two sets of d orbitals is denoted by ∆o or 10Dq.
 As the baricenter must be conserved on going from a spherical field
to an octahedral field, the t2g set must be stabilized as much as the eg
set is destabilized. The upper (eg) set goes up by 6Dq, and the lower
set (t2g) goes down by 4Dq.
 The actual size of the gap varies with the metal and the ligands.
__ __ eg
dz2 dx2-y2
0.6∆o ∆o
__ __ __ __ __
Spherical field
__ 0.4∆
__o __ t
2g
dxy dxz dyz
Octahedral field

11
d-orbital energy level diagrams
octahedral complex

d1 d2

d3

12
d-orbital energy level diagrams
octahedral complex
d4

high spin low spin

<P >P

d-orbital energy level diagrams

octahedral complex
d5

high spin low spin

<P >P

13
 d-orbital energy level diagrams
octahedral complex
d6

high spin low spin

<P >P

d-orbital energy level diagrams

octahedral complex
d7

high spin low spin

<P >P

14
 d-orbital energy level diagrams
octahedral complex
d8

d9

Crystal Field Splitting Energy (CFSE)

• In Octahedral field, configuration is: t2gx egy
• Net energy of the configuration relative to the average
energy of the orbitals is: = (–0.4x + 0.6y)O
O = 10 Dq

Beyond d3
• In weak field: O  P,  t2g3eg1
• In strong field O  P,  t2g4
• P - paring energy (PT = Pc + Pex)
Pc is Coulombic repulsion energy and Pex is exchange energy

15
 Illustration of CFSE
Illustration of CFSE
2 6
3+ 1 –
[Ti(H O) ] : a d complex and the e occupies the lowest energy
[Ti(H 2O)6 i.e.: one
orbital, ]3+ a of d1
complex anddegenerate
the three e-
the occupies the lowest
t orbitals. energy
The purple colour is a
orbital, i.e. one of the three degenerate t2g2gorbitals. The purple
result of the absorption of light which results in the promotion of this t2g
colour is a result of the absorption of light which results in the
electron into
promotion thet2g
of this level. t2g1into
eg electron eg0 
thet2g
eg0e 1
level.
g t2g1eg0 –> t2g0eg1

The The
UV-Vis absorption
UV-Vis absorptionspectrum
reveals that this transition
spectrum reveals that thisoccurs with a
maximum at 20300
transition occurscm –1
with which
a
corresponds
maximumtoat∆20300243 cm-1 which
kJ/mol.
o
corresponds to Do 243 kJ/mol.
cm–1
(1000(1000 cm=-1 11.96
= 11.96kJ/mol
kJ/mol oror
2.86
2.86kcal/mol or
kcal/mol or
0.124 eV)
0.124 eV.)

29
Typical D0 values are of the same order of magnitude as the energy of a chemical bond.

absorbed observed
color color

VIBGYOR

16
17
 d Orbital Splitting
The colors exhibited by most transition metal complexes
arises from the splitting of the d orbitals. As electrons
transition from the lower t2g set to the eg set, light in the
visible range is absorbed.

Complexes with d10 and d0 configuration are usually colorless:

Ex: Zn(H2O)6]2+; Cu(PPh3)4]+

MnO4–, Cr2O72– with d0 metals: are strongly colored !!

- Not the d-d transitions, rather due to ‘charge transfer’ transition.

∆o depends on:
• Nature of the ligands (L)
• The charge on the metal ion (M+)
• Whether the metal is a 3d, 4d, or 5d element

Ligands which cause a small splitting are Weak field ligands

(∆o in the range 7000 – 30000 cm–1) and those cause a large splitting
are Strong field ligands (CFSE typically > 30000 cm–1)

18
 Do is dependent on L:
∆o is dependent on L:

[CrCl6]3- 13640 cm-1 163 kJ/mol

[Cr(H2O)6]3+ 17830 213
[Cr(NH3)6]3+ 21680 314
260
[Cr(CN)6]3- 26280 314

[Co(NH3)6]3+ 24800 cm-1 163 kJ/mol

[Rh(NH3)6]3+ 34000 213
[Ir(NH3)6]3+ 41000 314
33

34

The Spectrochemical Series

Based on measurements for a given metal ion,

the following series has been developed:

I–<Br-<S2–<Cl–<NO3–<N3–<F–<OH–<C2O42–<H2O
<NCS–<CH3CN<pyridine<NH3<en<bipy<phen
<NO2–<PPh3<CN–<CO

But CFT never explain the basis of the Spectrochemical Series

19
 d Orbital Splitting
The splitting due to the nature of the
ligand can be observed and measured
using a spectrophotometer. Smaller
values of ∆o result in colors in the
green range. Larger gaps shift the
color to yellow.

The Spectrochemical Series

The complexes of cobalt(III) show the shift in color due to the ligand.

(a) CN–, (b) NO2–, (c) phen, (d) en, (e) NH3,
(f) gly, (g) H2O, (h) ox2–, (i) CO3 2–.

20
 ∆o depends on:
1. ∆o increases with increases going down a group
of metals. 3d< 4d < 5d e.g. Ni<Pd<Pt

2. ∆o increases with increasing oxidation number

on the metal.
Mn+2<Ni+2<Co+2<Fe+2<V+2<Fe+3<Co+3
<Mn+4<Mo+3<Rh+3<Ru+3<Pd+4<Ir+3<Pt+4
Oxidation state of the metal ion
[Ru(H2O)6]2+ 19800 cm-1
[Ru(H2O)6]3+ 28600 cm-1

In Tetrahedral Field
The ligands occupy the four
alternate corners of the cube
leaving the rest four corners
empty

21
In Tetrahedral Field

22
 Tetrahedral Field

∆t<∆o

∆t= 4/9 ∆o
• There are only 4 ligands in the tetrahedral complex, and so the
ligand field is roughly 2/3 of the octahedral field.

• As a result, all tetrahedral complexes are high-spin since the

CFSE is normally smaller than the paring energy.
• The direction of ligand approach in tetrahedral complex does not
coincide with the d-orbitals. This reduces the field by a factor of 2/3.
Therefore ∆t is roughly 2/3 × 2/3 = 4/9 of ∆o
• Hence low spin configurations are rarely observed. Usually, if a
very strong field ligand is present, the square planar geometry will
be favored.

23
 Octahedral vs.
Octahedral Tetrahedral
vs.Tetrahedral FieldsFields

46

What is the CFSE of [Fe(CN)6]3-?

CN– = s.f.l.
C.N. = 6  Oh Fe(III)  d5 H.S. L.S.
3-
eg eg
+ 0.6 o
– 0.4 o
t2g t2g

CFSE = 5 x –0.4 o + 2P = – 2.0 o + 2P

If the CFSE of [Co(H2O)6]2+ is –0.8 o, what spin state is it in?

C.N. = 6  Oh Co(II)  d7
H.S. L.S.

2+ eg eg
+ 0.6 o
– 0.4 o
t2g t2g

CFSE = (5 x –0.4 o) CFSE = (6 x –0.4 o)

+ (2 x 0.6 o) +2P = –0.8 o+2P + (0.6 oct) + 3P= - 1.8 o + P

24
 Spinels - Use of CFSE
Spinels - Use of CFSE
Spinel is the name given to the mineral MgAl2O4.
It has a common structural arrangement shared by many
oxides of the transition metals with formula AB2O4.
In the normal spinel
The oxygens form a cubic close packed array
The Mg(II) (A-type) sit in tetrahedral sites
The Al(III) (B-type) sit in octahedral sites
i.e. [MII]tet[MIIIMIII]ohO4
An inverse spinel is an alternative arrangement where half
of the trivalent ions swap with the divalent ions so that the
Mg(II) now occupy octahedral sites ie B(AB)O4.
i.e. [MIII]tet[MIIMIII]ohO4
19

Spinels -
Spinels - Use
UseofofCFSE
CFSE
There are several transition metal oxides which have the
formula AB2O4 and crystallize in spinel or inverse spinel
structure. E.g. FeCr2O4, ZnAl2O4, Co3O4, Mn3O4, Fe3O4,
NiFe2O4 etc.
CFSE is highly useful to determine whether a structure
would be normal or inverse

If M3+ ion has a higher CFSE in an octahedral field

compared to M2+ ion, normal spinel will result.
If M2+ ion has a higher CFSE in an octahedral field
compared to M3+ ion, inverse spinel will result.

normal [MII]tet[MIIIMIII]ohO4; inverse [MIII]tet[MIIMIII]ohO4

20

25
 Spinels - Use of CFSE
Example: Mn3O4 (oxygen weak field ligand)
Mn2+; d5 = t2g3eg2; no CFSE
Mn3+; d4 = t2g3eg1; 0.6 Do
Structure: Normal Spinel
Example: Fe3O4 (oxygen weak field ligand)
Fe2+; d6 = t2g4eg2; 0.4 Do
Fe3+; d5 = t2g3eg2; no CFSE
Structure: Inverse Spinel

How about MnCr2O4 and FeCr2O4 ? Work out.

Tip: If A2+ is d6, d7, d8, or d9 ion and B3+ is Fe3+, AB O is INVERSE
Tip: If A2+ is d6, d7, d8, or d9 ion and B3+ is Fe3+, AB2O4 is INVERSE
21

Special case II
Jahn-Teller Distortion
Special Case I: Jahn-Teller Distortion
If bot the eg orbitals are symmetrically repelled by 4 ligands
• Iffilled
both- the eg orbitals
all ligands are symmetrically
are repelled equally.
filled - allregular
Result: ligandsoctahedron
are repelled equally. repelled by
2 ligands
Result: regular octahedron dx2- y 2 dz 2
asymmetrically filled
• IfIfasymmetrically filled -- some
some ligands E
ligands are repelled
are repelled more than morethethan the.
other
other . Result: Distorted octahedron
Result: Distorted octahedron
Consider eg configuration:
Consider )1 2(d
(dz2(d
eg configuration: 2
)1 xd2–2y2) 2) 2
z x -y
Ligands
Ligandsalong x, –x,
along x, y,-x,–yy,will be repelled
-y will moremore
be repelled and bonds elongated.
and bonds elongated.
i.e. i.e.
the the
octahedron will be compressed along the z axis.
octahedron will be compressed along the z axis.
Consider eg configuration: (dz2)2 (dx2 –y2)1
Ligands along e+z,
Consider –z will be repelled
g configuration: (dzmore
2) dxand
2
2 y2bonds
1 elongated. i.e.
- )
the octahedron will be elongated along the z axis.
Ligands along z, -z will be repelled more and bonds elongated. i.e.
23
the octahedron will be elongated along the z axis.

26
 The Jahn-Teller Effect
Any non-linear molecular system in a degenerate electronic
state will be unstable, the complex will undergo distortion to
lower the symmetry and remove the degeneracy.

The Jahn-Teller effect predicts which structures will distort.

It does not predict the nature or extent of the distortion.
The effect is most often seen when the orbital degneracy is
in the orbitals that point directly towards the ligands.

The Jahn-Teller Effect

In octahedral complexes, the effect is most

pronounced in high spin d4, low spin d7 and d9
configurations, as the degeneracy occurs in the eg set of
orbitals.

d4 d7
d9 eg

t2g

27
 Special Special
case case
of II:
d8 dOctahedral
8 Octahedral

repelled by 4 ligands
Examples:
Examples: 2+ repelled by
Ni , Pd2+, Pt2+, Cu3+, Ag3+, Au3+ 2 ligands
Ni2+, Pd2+, Pt2+, Cu3+, Ag3+, Au3+ dz 2 dx2- y 2

Only when the ligand is very strong or CFSE is very high

dx2- y 2
dx2- y 2

dz 2
dz 2

E dx y
E
dxz, dyz

Square-planar complex is formed ; attempts to form octahedral

Square-planar complex is formed ; attempts to form
complexes become impossible 22
octahedral complexes become impossible

Jahn-Teller Effect
The Jahn-Teller Theorem was published in 1937 and states:

"any non-linear molecular system eg

x2–y2 z2
in a degenerate electronic state
will be unstable and will undergo z2 x2–y2
distortion to form a system of
lower symmetry and lower energy D
thereby removing the degeneracy"
xy xz yz
t2g

xz yz xy
z-elongation z-compression
2 long 4 short 24 long
short42short
long

28
 Jahn-Teller Effect
• Typical distortion of an octahedron leads to 4 + 2 coordination with
either 2 short or 2 long bonds
• JT effect can also occur for tetrahedrally coordinated species
• JT effect not very strong for “octahedral” compounds with degenerate
ground state involving incomplete occupancy of t2g orbitals

The Jahn-Teller effect predicts which structures will distort. It

does not predict the nature or extent of the distortion. The
effect is most often seen when the orbital degeneracy is in the
orbitals that point directly towards the ligands.

Most d8 metal ions form

square planar complexes.
Majority of complexes are
low spin (i.e. diamagnetic).
Examples: Pd2+, Pt2+, Ir+,
and Au3+.

29
 Crystal Field splitting for d-orbitals

56

Some examples of Jahn-Teller distorted complexes

CuBr2 4 Br at 240pm 2 Br at 318pm

CuCl2.2H2O 2 O at 193pm 2 Cl at 228pm 2 Cl at 295pm
CsCuCl3 4 Cl at 230pm 2 Cl at 265pm
CuF2 4 F at 193pm 2 F at 227pm
CuSO4.4NH3.H2O 4 N at 205pm 1 O at 259pm 1 O at 337pm
K2CuF4 4 F at 191pm 2 F at 237pm
CrF2 4 F at 200pm 2 F at 243pm
KCrF3 4 F at 214pm 2 F at 200pm
MnF3 2 F at 209pm 2 F at 191pm 2 F at 179pm

30
Crystal Field Theory: Color of Coordination Compounds

The energy gap between the eg

and t2g orbitals, O, (the crystal
field splitting) equals the energy
of a photon:
h = O = h= E

As O, varies, h will also vary

and the color of the compound
will change

Absorption of a photon causes a jump from a t2g to an eg orbital

Ligand substitutions and color changes: Ni2+

31
The spectrochemical series of color and magnetic properties:
weak field (red, high spin), strong field (violet, low spin)
Spectrochemical series
A d5 electron metal ion

Strong field Ligands Weak field Ligands

(violet, low spin) (red, high spin)

Color of complexes depend on O = h= E

O = h

“red “violet
absorption” absorption”
“looks green” “looks yellow

64

32