CHM102A

Lecture 5
Lecture5

Magnetic Properties of Coordination Complexes

Configuration
3dn,n
, n=

s+o= [L(L+1)+4S(S+1)]1/2B.M.

s.o.=[4S(S+1)]1/2B.M.
(calculated)

expt. B.M.
at 300K
at300K

3.0

1.73

1.7 1.8

4.47

2.83

2.8 2.9

5 20
5.20

3 87
3.87

3 7 3.9
3.7
39

5.48

4.90

4.8 5.0

5.92

5.92

5.8 6.0

5 48
5.48

4 90
4.90

5 1 5.7
5.1
57

5.20

3.87

4.3 5.2

4.47

2.83

2.9 3.9

3 00
3.00

1 73
1.73

1 7 2.2
1.7
22

10

0.00

0.00

If there is a possibility for contribution from the orbital angular momentum,

= [L(L+1) + 4S(S+1)]1/2
For a given value of the orbital quantum number l, the magnetic quantum number m can have any
values from l to +l and L = sum of m
For d orbital electrons, m = 2, 1, 0, -1, -2
If there is only one electron in the d orbitals, L = 2

Magnetic Properties of Coordination Complexes

Consider a Ni(II) complex, electronic configuration is d8
For a free metal ion,

S = 1, L = 3 and = [L(L+1) + 4S(S+1)]1/2 = 4.47 B.M.

For an octahedral complex,
Orbital contribution is zero and
magnetic moment is close to the spin
only value

For a tetrahedral complex,

Magnetic moment is higher than the
spin
i only
l value
l as there
h
i positive
is
ii
orbital contribution
3

Magnetic Properties of Coordination Complexes

d xy

d x 2-y 2

d yz

45

90

dxz

For an octahedral complex, orbital contributions are possible only when the t2g orbitals
are differentially occupied and for a tetrahedral complex the t2 orbitals have to be
4
differentially occupied.

Magnetic Properties of Coordination Complexes

Co(II) d7

K2CoCl4

moisture

Blue

[Co(H2O)6]Cl2
Pink

heat

t
No orbital contribution
Magnetic moment = 3.73 BM

Orbital contribution
Magnetic moment = 4.2 B.M.
higher than spin-only value

Colors
Coordinationchemistryinbiologicalsystems

Origin of color
Color is perceived in two different ways:
Additive mixing, where different colors made by combining different colors of
light
subtractive mixing, where different wavelengths of light are taken out so that
the light is no longer pure white
For colors of coordination complexes, subtractive mixing is considered.
subtractive mixing is that white light (which is made from all the colors mixed
t
together;
th VIBGYOR) interacts
i t
t with
ith an object.
bj t
Few of them gets absorbed and the remaining is coming out (see the below
p
picture)
)

absorbs wavelenght of light

yellow and green

Example for Subtractive mixing

emitted wavelength
of light

Colors

The electronic spectrum of the [Ti(H2O)6]3+

eg

eg

Energy

eg

Color observed: purple

t2g

t2g

t2g

Absorption:
20,300 cm-1 (243 KJ/mol)

Absorption spectrum of [Ti(H2O)6]3+

10

Laporte Rule
In a molecule or ion possessing center of symmetry, transitions are not allowed
between orbitals of same parity. Transitions are only possible between orbitals that
differ byy l = 1;; l is the orbital qquantum number.
Examples of forbidden transitions are: s to s, d to d, p to f etc.
Tetrahedral geometry is not affected by this rule as it does not have a center of
symmetry.
As a consequence,
conseq ence for tetrahedral complexes
comple es are 100 times more than the for
octahedral complexes.
Even octahedral complexes lose their center of symmetry transiently due to
unsymmetrical vibrations. This leads to color in octahedral and square planar
complexes

11

Spin-forbidden and Spin-allowed Transitions

Any transition for which S0 is strongly forbidden; that is, in order to be allowed, a
transition must involve no change in spin state.
state

ENERGY

G.S
SG.S. = 1/2

ENERGY

E.S
SE.S. = 1/2

S = SE.S. - SG.S. =0; Allowed

G.S
SG.S. = 0

E.S
SE.S. = 1

S = 1. 0; Forbidden

2 has a d5 metal ion and is a high-spin complex. Electronic transitions are

[Mn(H2O)6]2+
not only Laporte-forbidden, but also spin-forbidden. The dilute solutions of Mn2+
complexes are therefore colorless.

G. S. : ground state; E. S. : exited state;

12

The electronic spectrum of the [Ti(H2O)6]3+

d z2

3+

OH 2

eg
dx2-y 2

d xz

d yz

t2g
dxy

H 2O

OH 2

Ti

Ti
OH 2

H 2O

OH2

H 2O

OH2

3+

H 2O

OH 2

M L symmetrical
M-L
has centre of symmetry

OH 2
OH 2

M L unsymmetrical
M-L
no centre of symmetry

9 Laporte forbidden
9 Spin allowed
9 Transitions allowed due to
vibronic coupling

Color observed: p
purple
p

9Occurs due to unsymmetrical

conformation in oh

Absorption:
20,300 cm-1 (243 KJ/mol) Absorption spectrum of [Ti(H O) ]3+
2
6

13

Color and CFT

Color effect based on the charge of metal ion

14

Ligand effect on Color and CFT

[Cr(NH3)6]3+

Strong ligands,
ligands leading to
high o. Absorbs violet
and appears yellow.

[Cr(NH3)5Cl]2+

Relatively weak set of ligands,

ligands
leading to reduced o. Absorbs
yellow and appears magenta.

15

MagnitudeofCFSplitting()

Color of the Complex depends on magnitude of

1. Metal: Larger metal J larger
Higher Oxidation State J larger
2. Ligand
Ligand:: Spectrochemical series

Cl- < F- < H2O < NH3 < en < NO2- < (N(N-bonded) < CNWeak field Ligand:
Ligand: Low electrostatic interaction: small CF splitting.
High field Ligand
Ligand:: High electrostatic interaction: large CF splitting.

3
[C F6]3
[CrF

3+ [Cr(NH
3+ [Cr(CN)
3
[C (H2O)6]3+
[Cr(H
[C (NH3)6]3+
[C (CN)6]3

Spectrochemical series: Increasing 16

Colors of Coordination Complexes with different geometry

Co(II) d7

K2CoCl4

moisture

Blue

[Co(H2O)6]Cl2
Pink

heat

17

The Laporte selection rule

d x 2 -y 2

Gerade symmetry

f bidd
forbidden

Octahedral

xy

Gerade symmetry
Tetrahedral
no centre
t off inversion
i
i
Laporte selection rule relaxed
due to d-p mixing
18

Comparative intensities of electronic transitions

Transitiontype

Example

Comparativeintensity

Spinforbidden
Laporte forbidden

[Mn(OH2)6]2+

Spinallowed
(centerofsymmetry)
Laporte forbidden

[Co(OH2)6]2+

101

[CoCl4]2

5 X10
X 102

[MnO4]

104

Spin allowed
(no center of symetry)
(nocenterofsymetry)
Laporte forbidden
Spinallowed
Laporte allowed
(chargetransfer)

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d0 and d10 ions have no d-d transitions

Certain complexes such as [MnO4]-, [CrO4]2- etc are intensely colored even though they
have metal ions without electrons in the d orbitals.
orbitals The color of these complexes are not
from d-d transitions, but from charge-transfer from ligand to metal orbitals (LMCT).

Zn2+

d10 ion

white

TiF4

d0 ion

white

TiCl4

d0 ion

white

TiBr4

d0 ion

orange

TiI4

d0 ion

darkbrown

[MnO4] Mn(VII) d0 ion

extremelypurple

d0 ion

brightorange

[Cu(MeCN)4]+ Cu(I)

d10 ion
ion

colourless

[Cu(phen)2]+ Cu(I)

d10 ion

darkorange

[Cr2O7] Cr(VI)

(LMCT)

20