Thermolysis mechanism of monoalkylplatinum(II) complexes with tertiary phosphine ligands. Methyl radical elimination from trans-Pt(I)(CH3)[P(CH3)3]2.

Thermolysis of the complexes trans-Pt(I)(Me)(PR3)2 (R = CH3, CD3, C2H5, C6H5, C6H11, Me = CD3) 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.