REACTIONS OF SOME PLATINUM YLIDES, INCLUDING A REARRANGEMENT TO A PLATINACYCLOBUTANE

Article abstract of DOI:10.1016/0022-328X(84)80317-4

The platinum(II) ylides (py)> (X = Cl, Br; py = pyridine) react with triphenylphosphine to give (PPh3)>.Oxidative addition of iodomethane gives (py)>, the NMR spectra of which indicate restricted rotation about the CH-CH2 bond in the ylide moiety, and addition of chlorine gives (py)>.Thermal decomposition of these ylides in the solid phase gives propene as the only hydrocarbon product, with CH3Cl or CH3Br from the iodomethane adducts.However, thermal or photochemical decomposition in dimethylsulphoxide solution gives considerable yields of ethylene (up to 95percent of the volatile products), the precursors of which are probably positive platinum ylide ions from dissociation of a halide ligand.The reaction of HI with (py)> in benzene solution leads to formation of a platinacyclobutane ^-+.Reaction with PhSH is unusual in that ethane is produced.