Molecular orbital studies of platinum olefin and acetylene complexes: reactions and reaction mechanisms

Abstract

Relative energies of platinum olefin and acetylene complexes, obtained from non-iterative semi-empirical one-electron molecular-orbital (NISEMO) calculations, are in qualitative agreement with available experimental results. Based on a synthesis of these calculations and the experimental results, mechanisms are proposed for (a) olefin–vinyl rearrangement, (b) HCl addition to π-bonded acetylene, and (c)π-bonded acetylene–acetylide-hydride rearrangement. This method provides a reasonable and economical approach to predicting the mechanisms and courses of reaction of fairly large molecules.