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Question -

Discuss the nature of bonding in thefollowing coordination entities on the basis of valence bond theory:




Answer -

(i) [Fe(CN)_6]_4−

(ii) [FeF_6]_3−

(iii) [Co(C_2O_4)3]_3−

(iv) [CoF_6]_3−

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_Answer

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(i) [Fe(CN)6]4−

In the above coordination complex, ironexists in the +II oxidation state.

Fe2+ :Electronic configuration is 3d6

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Orbitalsof Fe2+ ion:

As CN isa strong field ligand, it causes the pairing of the unpaired 3d electrons.

Sincethere are six ligands around the central metal ion, the most feasiblehybridization is d2sp3.

d2sphybridizedorbitals of Fe2+ are:

6electron pairs from CN ions occupy thesix hybrid d2sp3orbitals.

Then

Hence, the geometry of the complex isoctahedral and the complex is diamagnetic (as there are no unpaired electrons).

(ii) [FeF6]3−

In this complex, the oxidation state of Fe is+3.

Orbitalsof Fe+3 ion:

Thereare 6 F ions. Thus, it will undergo d2spor sp3d2 hybridization.As F− is a weak field ligand, it does not cause thepairing of the electrons in the 3d orbital. Hence, the mostfeasible hybridization is sp3d2.

sp3d2 hybridizedorbitals of Fe are:

Hence, the geometry of the complex is foundto be octahedral.

(iii) [Co(C2O4)3]3−

Cobalt exists in the +3 oxidation state inthe given complex.

Orbitals of Co3+ ion:

Oxalateis a weak field ligand. Therefore, it cannot cause the pairing of the 3orbitalelectrons. As there are 6 ligands, hybridization has to be either sp3d2 or d2sp3 hybridization.

sp3d2 hybridization of Co3+:

The 6electron pairs from the 3 oxalate ions (oxalate anion is a bidentate ligand)occupy these sp3d2 orbitals.

Hence, the geometry of the complex is foundto be octahedral.

(iv) [CoF6]3−

Cobalt exists in the +3 oxidation state.

Orbitalsof Co3+ ion:

Again,fluoride ion is a weak field ligand. It cannot cause the pairing of the 3d electrons.As a result, the Co3+ ion will undergo sp3d2 hybridization.

sp3d2 hybridizedorbitals of Co3+ ion are:

Hence, the geometryof the complex is octahedral and paramagnetic.

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