Mechanism of thermolysis of monoalkylplatinum(II) complexes with tertiary phosphine ligands. Methyl radical elimination from trans-Pt(I)(CD 3)[(P(C 3) 2] 2

Abstract

Thermolysis of the complexes trans-Pt(I)(Me)(PR 3) 2 (R = CH 3, CD 3, C 2H 5, C 6H 5, C 6H 11, Me = CD 3) in deuterated or non-deuterated hydrocarbons at 120°C produces MeH and/or MeD. Appropriate isotopic labeling has revealed the existence of two decomposition pathways. The main route involves homolytic splitting of the platinum-methyl bond to give methyl radicals, which then form methane by abstraction of hydrogen from the R groups of the phosphines or from the solvent. The second, less important, route has a molecular mechanism involving coordinate methyl groups.