High-pressure pulse radiolysis as a tool in the study of transition metal reaction mechanisms.

The unique combination of high-pressure and pulse radiolysis kinetic techniques enables detailed mechanistic insight for a large variety of chemical processes to be gained. Typical examples for transition metal reactions are presented. These include ligand substitution, electron transfer, reactions of complexes with uncommon oxidation states, and reactions with radicals, including the formation and decomposition reactions of complexes with metal-carbon sigma bonds. The volumes of activation and volume profiles obtained form the basis of a critical analysis of different plausible reaction mechanisms.