Inorganic Chemistry 3
Inorganic Chemistry 3
Inorganic Chemistry 3
Complexes
The shapes of the transition metal complexes are affected by
whether the d -orbitals are symmetrically or asymmetrically filled
Symmetrical electronic configuration: d 0, d 3, d 5 (weak field),
d 6 (strong field), d 8 , d 10 .
d-electrons repel electrons of ligands equally
The effect is more for eg orbitals (as they are directly facing ligands) than
t2g orbitals.
The distortion caused by asymmetric t2g orbitals is usually small.
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Symmetrical electronic arrangement
2
Asymmetrical electronic arrangement
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Tetragonal Distortion contd…
eg orbitals if asymmetrically filled
no longer remain degenerate
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Jahn-Teller Theorem
Hermann Arther Jahn and Edward Teller stated that for a nonlinear molecule in
an electronically degenerate ground state distortion must occur to lower the
symmetry, remove degeneracy and lower energy– known as Jahn-Teller Theorem
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Structural effects of Jahn-Teller
distortion
All six Ni-O bonds two long axial
equal at 2.05 Å Cu-O bonds
= 2.45 Å
four short
in-plane
Cu-O bonds
= 2.00 Å
[Ni(H2O)6]2+ [Cu(H2O)6]2+
no J-T distortion J-T distortion lengthens axial Cu-O’s
The Jahn-Teller Theorem contd..
When in weak ligand field When the ligand field is significantly strong
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Square planar arrangement
In case of d 8 configuration t2g6 eg2 and the arrangement is symmetrical
BUT this is applicable only for weak field e.g. [Ni(H2O)6]2+ or [Ni(NH3)6]2+
In strong field: An electron in dx2--y 2 gets repelled by four ligands
whereas an electron in dz2 gets repelled by only two ligands
Thus eg orbitals do not remain degenerate (Jahn-Teller distortion)
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Square planar arrangement
dd
d
d
d
d
d
d
dxz, dyz
dxz, dyz
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Square planar complexes contd …
Square planar complexes are formed
With strong field ligands for 1st and other row elements
Metals at higher oxidation state
Even with weak field ligands for 2nd and 3rd row elements
• Mainly d 8 and d 9 systems form square planar complexes (e.g. Pt(II), Au(III))
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