Electronic Spectra of Transition Metal Complexes Spectra arises because, 1.

electrons may be promoted from one energy level to another. 2. Such electronic transition require high energy. 3. During electronic transitions low energy vibrational and rotational transition will always occur 4. In electronic spectra such transitions are too close in energy to be resolved into separate absorption bands. 5. But they cause broadening of absorption bands in dd-d spectra 6. BandBand-widths are in the order of 1000 1000-3000 cm-1.
Spectrum of a coloured solution may be measured quite easily using a spectrophotometer Monochromatic beam of light is passed through a solution on to a photo electric cell. Amount of light absorbed at any particular frequency can read off, or a whole frequency range can be scanned.

Absorbance is plotted,

Io

The absorbance A is called optical density which is give by A = log ( I )

Io = Intensity of the original beam of light I = Intensity after passing through the solution

the molar absorption coefficient (molar absorptivity coefficient) calculated from A

= A/Cl

C = concentration of the solution in moles l = path length in cms (1 cm long)

Selection rules
Not all the theoretically possible electronic transitions are actually observed. observed. Selection rules are there to distinguish between allowed and forbidden transitions. transitions. Allowed transitions occur, forbidden do occur, but much less common, low intensity. intensity.

Laporte Selection (orbital) rule:

Transition which involve a change in the subsidiary Q. No. l = 1 are Laporte allowed and have high absorbance.

e.g. Ca s2p0

s1p1

l Changes by +1, = 50005000-10000 lit mol-1 cm-1 In contrast dd-d transitions are forbidden as l = 0 ( ( = 5 5-10 lit mol-1 cm-1) Spin selection rule: During the electronic transition electron does not change its spin, i.e. s = 0
In [Mn(H2O)6]2+, d d-d transitions are spin forbidden; WHY?

d-d transitions are forbidden ( (Laporte Laporte forbidden) as l = 0 Low absorbance ( = 5 5-10 l mol-1 cm-1) Because of a slight relaxation in Laporte rule, d d-d transitions are observed. When transition metal forms a complex, M is surrounded by L ligands. ligands. Mixing of dd- and p p-orbitals may occur and as a result, they are no longer true dd-d in nature Mixing is common when complexes lack centre of symmetry Intensity ( value) of absorption increases if the mixing is more effective. e.g. [MnBr4]2- is tetrahedral [Co(NH3)5Cl]2+ is octahedral with unsymmetrical substitution, are coloured e.g. [Co(NH3)6]3+ or [Cu(H2O)6]2+ have center of symmetry, no mixing of
orbitals, are not coloured However, the M-L bond vibrates so that the ligand spends an appreciable amount of time out of their centrosymmetric equilibrium position, as a result, small amount of mixing occurs and low intensity transitions are observed. p & d-

Many Mn2+ are offoff-white or palepale-flesh coloured and the intensity is only 1/100th of that of spinspin-allowed transitions. Spin-forbidden transitions are weak and can be ignored. SpinThus analyses of spectra of transitions metal complexes are greatly simplified by ignoring all spinspin-forbidden transitions. Thus for d2 only terms that are need to be considered are Ground State 3F and the excited state 3P.

Splitting of electronic energy levels and spectroscopic states s are symmetrically spherical and unaffected in an Oh field p orbitals are directional and are affected by an Oh field (all are affected equally and no splitting)
eg eg 10Dq t2g t2g triply degenerate
4Dq dooubly degenerate 6Dq

Laporte
Allowed Partly allowed* *
Some p - d mixing

Spin
Allowed Allowed Allowed Forbidden Forbidden

Type of Spectra
CT

10000 500 8 - 10 4 0.02

Example

[TiCl6]2[CoX4]X = Br, Cl
[Ti(H2O)6]3+, [V(H2O)6]3+ [MnBr4]2[Mn(H2O)6]2+

d-d d-d d-d d-d

Forbidden Partly allowed* * Forbidden

For d1 ground state is a 2D state; T2g and Eg are spectroscopic states

Eg

+6 -4

T2g

A set of f orbitals will split into three levels in an octahedral field

A 2g
12 Dq Single

2 Dq 6 Dq

T2g T1g
Triply degenerate

Spectra of d1 and d9 ions In a free gaseous metal ion, d orbitals degenerate and no dd-d transitions are observed. In a complex, degeneracy is lost and splits into t2g (t2) and eg(e) Let us consider [TiCl6]3- or [Ti(H2O)6]3+
A B S O R B A N C E
0 3000

d1 system

20300 cm-1

2000

[Ti(H2O)6]3+

1000 (cm-1)

Magnitude of o depends on the nature of the ligands and affects the energy of electronic transitions and hence the frequency of absorption maxim

[TiCl6]3[TiF6]3[Ti(H2O)6]3+ [Ti(CN)6]3-

13,000 cm-1 18,900 cm-1 20,300 cm-1 22,300 cm-1

d1, d6, d4,d9 one dd -d d2, d7, d3,d8 three dd -d

Spectrochemical series, ligand field strength Extent of splitting is related to the ligand positions in the spectrochemical series Let us consider a d9 system Let us consider d9 system: e.g. [Cu(H2O)6]2+ Splitting of dd-orbitals is similar to d1 case In d1, one electron is there in t2g level In d9, one hole is there in eg level

In d1, promotion of one electron from T2g Eg, whilst in d9 it is simpler to consider the promotion of an electron as the transfer of a hole from Eg T2g

For d9 inverse of d1 energy diagram holds good

T2g
2

4 Dq 6Dq

Eg

d1and d9 in Tetrahedral Field: Exactly reverse of that of Oh field

T2
2

D
E

Octahedral High Spin complexes

d1

d6

d4

d9

Tetrahedral High Spin complexes

d1

d6

d4

d9
is it true???

Terahedral complexes are always high high-spin

d1 & d6 ; d4 & d9 d4 & d9 ; d1 & d6

Octahedral Tetrahedral

All these cases can be combined into a single diagram called Orgel diagram, which describes the qualitative way of the effect of electronic configuration with
i) ii) iii) iv) One electron One more electron than a half half-filled shell One less electron than a full full-shell One less than a half half-filled shell

d1 & d6 Tetrahedral

T2g (T2)

Eg (E) d1 & d6 Octahedral

d4 & d9 Octahedral Eg (E)

Increasing ligand field

T2g (T2) d4 & d9 Tetrahedral 0

Spectra of d2 and d8 ions In an octahedral field t2g2eg0 Two possibilities: Electron may be promoted from dxz or dyz to dz2 or dx2-y2 Less energy is needed to promote an electron to dz2 than dx2-y2 (dxy)1(dz2)1 less energy (dxy)1(dx2-y2)1 more energy for transition Electrons are confined xy plane, as a result more electronelectron -electron repulsion t2g1eg1

Electrons are spread around in all three directions x, y & z reducing the electronelectron-electron repulsion

In both the cases electrons are promoted and another high energy state will be formed. Thus four energy levels will be there

For d2: G.S. Term 3F and four excited states:

3P, 1G, 1D

& 1S

Ground State contains 2 electrons with parallel spins. But the 1G, 1D & 1S states contain electrons with opposite spins and are ignored.

3F

and 3P can have transitions A2g + T1g + T2g

p-orbitals are not split, 3F

Thus three transitions are possible

Let us consider [V(H2O)6]3+

d2 system

1.2 o
Molar absorbance M

10

T 1g
3

T1g(P)
3

T 1g

A2g T 1g
3

T2g

0.2 o

-0.8 o
30000 20000 10000 cm-1 Electronic spectrum of [V(H 2O) 6]3+ : d 2system 40000

Ligand field strength of H2O results in transitions occurring close to the crosscross-over point between 3T1g(P) and 3T2g(F) and they are not resolved. V3+ ion with three different ligands will show three distinct peaks.

In case of Ni2+, a d8 system with two holes in eg Promoting one or two electrons to eg means transferring the hole(s) to t2g level
3P

is not split and 3F is split into three states and will be inverted will be the Ground State Term

3A 2g

Similarly, d7 is similar to d2 and d3 is similar to d8 in an octahedral environment Cr3+, a d3 system is expected to show three peaks
All these cases can be combined into a single diagram called Orgel diagram, which describes the qualitative way of the effect of electronic configuration with i)two i)two electron ii)two ii)two more electron than a half half-filled shell iii)two iii)two less electron than a full full-shell iv)two iv)two less than a half half-filled shell

Octahedral High Spin complexes

d2

d8

d3

d7

Tetrahedral High Spin complexes

d3

d7

d8

d2

Combined Orgel diagram d2 tetrahedral 3T1g (P)

3P

3A 2g 3T 1g (P)

d2 octahedral d7 octahedral d3 tetraahedral

d7 3T 1g (F) tetrahedral d3 3T 2g octahedral d8 3A octahedral 2g

3F

3T

2g

3T

1g (F)

d8 tetrahedral

Increasing ligand field

10

Molar absorbance

3A

2g

3 T (P) 1g

3A

2g

3 T (F) 1g 3A 2g

3 T (F) 2g

30000 20000 10000 cm-1 Electronic spectrum of [Ni(H 2O)6]2+ : d 8system

40000

Combined Orgel diagram d2 tetrahedral 3T1g (P)

3P

3A 2g 3T 1g (P)

d2 octahedral d7 octahedral d3 tetraahedral

d7 3T 1g (F) tetrahedral d3 3T 2g octahedral d8 3A octahedral 2g

3F

3T

2g

3T

1g (F)

d8 tetrahedral

Increasing ligand field

We have two 3T1g states one each for 3P and 3F state Both T1g states are curved, because they have the same symmetry, and they interact with each other

Interelectronic repulsions lowers the energy of the lower states and increases the energy of the higher state.

The effect is much more marked on the left of the diagram because two levels are close in energy

If the lines have been straight, they would cross each other which implies that at crosscross-over two electrons in one atom have the same symmetry and the same energy

This is impossible; prohibited by nonnon-crossing rule. State of same symmetry cannot cross each other

The mixing or interelectronic repulsion which causes the bending of the lines is expressed by Racah Parameters B and C. B and C can be calculated from liner combination of exchange intetrals and Coulomb integrals But they are obtained emperically from the spectra of the free ions.
with mixing
4 4P

noo mixing

T 1g(P)

15B
4

6Dq
4

8Dq

T 1g (F)

F
4

T 2g A 2g

12Dq

10Dq

The splitting of the 4P, 4F states in Cr3+

For transition between the same multiplicity states B is enough to explain the positions of the bands. For different multiplicity we need both B and C. In d3, for V2+ ion, separation between 4F and 2G is 4B + 3C B ~ 700700-1000 cm-1 and C is ~4B

Let us consider d3 (Cr3+) ion, B and C are known; B = 918cm-1, C = 4133 cm-1 The possible transitions are observed
4A 2g 4A 2g 4A 2g 4T 4T 4T 2g 1g 1g

predicted 14900 (10 Dq) Dq) 26800 (18 Dq) Dq) 30700 (12Dq + 15B)
with mixing
4

Racah Parameter B for M. ions in cm-1 Metal Ti V Cr Mn M2+ 695 755 810 860 917 971 1030

T.

1 = 14900 (F) (P) 2 = 22700 3 = 34400

M3+ 861 918 965 1015 1065 1115

P 15B

noo mixing

T 1g(P)

Fe Co

3
4

Ni

6Dq
4

8Dq

T 1g (F)

F
12Dq 10Dq

3
4T 2g

Due to the mixing of P and F terms, energy of 4T1g(P) increased by an amount x 4T (F) and that of 1g decreased by an amount x.

A 2g

The splitting of the 4P, 4F states in Cr3+

B relates to a free ion, the apparent value of B in a complex is always less than that of a free ion value because electron on the metal can be delocalized into MOs covering both metal and the ligands

Use of B improves the agreement. This delocalization is called nephelauxetic effect and nephelauxetic ratio is given be = B/B. decreases as delocalization increases, always, <1, B ~ 0.70.7-0.9 B If all the transitions are there, then 15B = 3 + 2 - 31 i.e. 15B = (15 +2) + 18 -30

With correction, better correlation between observed and improved theoretical results
with mixing

observed
4A 2g 4A 2g 4A 2g 4T 2g 4T 1g 4T 1g

corrected (theoretical)

4P

noo mixing

4T

1g (P)

1 = 14900 14900 (10 Dq) Dq) (F) (P) 2 = 22700 22400 (18 Dq - x) 3 = 34400 34800 (12Dq + 15B + x)

15B
6Dq
4F

x 8Dq

4T

1g

(F)

4T

2g 2g

12Dq

10Dq

4A

The splitting of the 4P, 4F states in Cr3+