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A molecular orbital study of insertion reactions in hydro-platinum(II) complexes

1976; Elsevier BV; Volume: 41; Issue: 1 Linguagem: Inglês

10.1016/0021-9517(76)90200-1

1090-2694

David R. Armstrong,

Carbon dioxide utilization in catalysis

Abstract The reaction mechanisms for selected insertion processes involving the hydrido-platinum(II) complex trans-Pt(PH3)2HCl have been studied by an all-valence-electron molecular orbital method. Optimized reaction coordinates have been elucidated for the insertion of CS2, CO2, and C2H4 into the metal-hydrogen bond and the results correlated with available experimental data. Following the entry of the reacting ligand into the coordination sphere of the metal, transition state and subsequent product formation appear to be largely dependent on steric effects. The sensitivity of the activation energies for reaction to specific ligands is rationalized in terms of the bonding patterns associated with the different ligands.