Thermal dimerization of 1-substituted-3,4-dimethylphospholes within the coordination sphere of platinum(II)

An analysis of the thermal dimerization reaction of 1-substituted-3,4-dimethylphosphole platinum(II) complexes reveals that the reaction mechanism involves branching and yields oxomethylene analogues as end products. The 1,4-butanedyl biradical is the common intermediate that causes the branching. The precursor complex has to have cis geometry for reaction initiation as the trans geometry prevents intramolecular C-C bonding. The halide characteristic affects the complex geometry only.