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Nickel allyl complexes

Topic no : 18

introduction
Bond between nickel and allyl( H2 C =CHCH2--) Hapticity can be 1 or 3 .

Mostly known complexes are of 3


Nickel complexes follow 16 electron rule. Example:nickel bis allyl complex

preparation

NiCl2 + 2C6H5MgBr Ni(CO)4 + H2C=CHCl

*Ni(3--C3H5)2] + MgBr2 + MgCl2

NiCl(3- C3H5) + 4CO

Physical properties
They are pyrophoric and moisture sensitive Infrared spectral studies
1. C=C antisymmetric at 1460/cm 2. C=C stretching vibration at 1020/cm.

Behave as an electron rich ligand

Chemical properties
1.INSERTION REACTIONS Ni(3-C3H5) + CO2 Ni(3-C3H5)( OCOC3H5)

lactone

2.Metal exchange reaction


[NiX(3-C3H5)2+ + 2Hg
[NiX(3-C3H5)2] + NaCo(CO)4

2Ni + 2Hg(1- C3H5)X


[Co(CO)3(3-C3H5)]

Co(CO)2(PPh3)( 3-C3H5)

- donor(filled) combines with the metal s.dz2 and pz orbitals because of similarity in symmetry

2 combines with the metal py and dyz orbitals

dxz of metal overlaps with 3 of allyl to form back bond

In case of back bonding,the strength of bond depends upon Efficiency of overlap Energies of orbitals

More effective is the overlap more efficient is the back bonding or donation of electrons from filled orbitals of metal to empty antibonding orbitals of ligand.