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Lecture 3

The document discusses orbital degeneracy versus electronic degeneracy in transition metal complexes. It explains that complexes with distorted octahedral geometry form when ligands are of different kinds. The Jahn-Teller effect causes complexes to distort if their electronic ground state is degenerate in order to remove the degeneracy and lower energy. This effect is observed in d9 copper complexes but not d8 nickel complexes. Distortions are more pronounced when degeneracy occurs in eg orbitals and for d1 complexes compared to d9 complexes. Site preferences in spinel compounds are also discussed.

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Areeb Ahmad
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92 views23 pages

Lecture 3

The document discusses orbital degeneracy versus electronic degeneracy in transition metal complexes. It explains that complexes with distorted octahedral geometry form when ligands are of different kinds. The Jahn-Teller effect causes complexes to distort if their electronic ground state is degenerate in order to remove the degeneracy and lower energy. This effect is observed in d9 copper complexes but not d8 nickel complexes. Distortions are more pronounced when degeneracy occurs in eg orbitals and for d1 complexes compared to d9 complexes. Site preferences in spinel compounds are also discussed.

Uploaded by

Areeb Ahmad
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Orbital Degeneracy versus Electronic Degeneracy

Distortions in Octahedral Geometry


L

L L
M
L L

L
Regular Octahedron: Complexes with regular octahedral geometry are expected to 
form, when all of the ligands are of the same kind

Distorted Octahedron: Complexes with distorted octahedral geometry are expected to


form, when the ligands are of different kinds
Distortions in Octahedral Geometry
If the ground electronic configuration of a non-linear complex is electronically
degenerate, the complex will distort so as to remove the degeneracy and
achieve a lower energy. This is called the Jahn-Teller Effect

d8 d9

eg eg

t2g t2g

Ni2+: Only one way of Cu2+: Two ways of filling the eg orbitals;
filling the orbitals; not there is degeneracy and Jahn-Teller
degenerate and no Jahn- Distortion is observed
Teller Distortion
Distortions in Octahedral Geometry
Jahn-Teller Distortion in Cu(II) Complexes

dx2-y2

eg
energy
dz2

dxy
t2g

Cu(II) in regular octa- dxz dyz


hedral environment [CuF6]4-
Cu(II) after J-T distortion
Jahn-Teller Distortion in d9 Complexes

Δo >> δ1 > δ2.
Jahn-Teller Distortion in d1 Complexes

dz2
eg
energy
dx2-y2

dxz dyz
t2g

d1 in regular octa- dxy


hedral environment
d1 after J-T distortion
d1 Vs d9

d9 d1

Distortions are more pronounced if the degeneracy occurs in an eg orbital
Distortions in Low-Spin Complexes

  


Distortions in High-Spin Complexes

 

 
Site Preference in Spinels
Spinel – MgIIAlIII2O4
AIIBIII2O4

The oxide ions form a close packed arrangement with octahedral and tetrahedral voids
and the metal ions occupy the voids.

Normal Spinels: (AII)tet(BIII2)octO4


The divalent AII ions occupy the tetrahedral voids, whereas the trivalent BIII ions
occupy the octahedral voids in a close packed arrangement of oxide ions.
MgAl2O4, Mn3O4, ZnFe2O4, FeCr2O4

Inverse Spinels: (BIII)tet(AIIBIII)octO4


The AII ions occupy the octahedral voids, whereas half of BIII ions occupy the
tetrahedral voids.
Fe3O4, CoFe2O4, NiFe2O4
Site Preference in Spinels

NiFe2O4

Ni is in +2 oxidation state and has 8 electrons in the d orbitals


In a tetrahedral void,
Configuration – e4t24; CFSE – 0.8 Δt (0.4 Δo)
In an octahedral void,
Configuration – t2g6eg2; CFSE – 1.2 Δo
Fe is in +3 oxidation state and has 5 electrons in the d orbitals
In a tetrahedral void,
Configuration – e2t23; CFSE – 0
In an octahedral void,
Configuration – t2g3eg2; CFSE – 0

Hence, it is advantageous to have Ni2+ ion in the octahedral voids. This results in an
inverse spinel structure for the compound.
FeIII[NiIIFeIII]O4
Site Preference in Spinels

Mn3O4

When Mn is in +2 oxidation state, it has 5 electrons in the d orbitals


In a tetrahedral void,
Configuration – e2t23; CFSE – 0
In an octahedral void,
Configuration – t2g3eg2; CFSE – 0
When Mn is in +3 oxidation state, it has 4 electrons in the d orbitals
In a tetrahedral void,
Configuration – e2t22; CFSE – 0.4 Δt (0.2 Δo)
In an octahedral void,
Configuration – t2g3eg1; CFSE – 0.6 Δo

Hence, it is advantageous to have Mn3+ ions in the octahedral voids. This results in a
normal spinel structure for the compound.
MnII[MnIII]2O4
Origin of Color

The Beer-Lambert Law


A = log10(Io/I) = εcl
where ε is the molar extinction coefficient ( in L cm-1 mole-1 ), c is concentration in mole L-1
and l is the path length in cm. A is known as ‘Absorbance’ and it is dimensionless.
Color of [Ti(H2O)6]3+

Absorption at 520 nm
gives the complex its
purple color

A more resolved absorption spectrum of the complex has a shoulder


Color and CFT
Color and CFT

[Cr(NH3)6]3+ [Cr(NH3)5Cl]2+

Strong ligands, leading to Relatively weak set of ligands,


high Δo. Absorbs violet leading to reduced Δo. Absorbs
and appears yellow. yellow and appears magenta.
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 by Δl = ±1; ‘l’ is the orbital quantum 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, ε for tetrahedral complexes are 100 times more than the ε 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

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