MECHANISM OF THERMOLYSIS OF MONOALKYLPLATINUM(II) COMPLEXES WITH TERTIARY PHOSPHINE LIGANDS. METHYL RADICAL ELIMINATION FROM trans-Pt(I)(CD3)2

Article abstract of DOI:10.1016/S0022-328X(00)99284-2

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 deg 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.