Abstract
The i.r. characterization of supported NiI trialkylphosphine (TAP) complexes NiI(TAP)n(n < 3) is performed using a CO probe molecule. The affinities of NiII and NiI ions for CO are compared. It is evidenced that TAP is a stronger ligand than CO: NiI(TAP)n(n < 3) complexes cannot coordinate more than one CO ligand at low CO pressure, whereas phosphine-free NiI complexes can coordinate two CO molecules. The increase of electron density on the metal ion causes a shift downwards of the νco frequency, proportional to the number and to the basicity of TAP ligands. It also produce a weakening of the M—CO bond, resulting in the easier removal of CO.
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