The reaction of [PtMeX(COD)] with 2-(diphenylphosphino)pyridine (Ph2Ppy) in 1 : 2 stoichiometry yields [PtMeX(Ph2Ppy)2] (X = Me, Ia; Cl, Ib; or I, Ic). Reaction of [PtMeCl(COD)] with one equivalent of Ph2Ppy gives the dinuclear complex [PtMeCl(Ph2Ppy)]2 (II). Several reactions of Ib have been studied. Treatment of Ib with NaY gives the cationic complexes [PtMe(η2-Ph2Ppy)(Ph2Ppy)][Y] (Y = BPh4, Id or BF4, Ie). The crystals of Id are triclinic, space group P1 with two molecules in a unit cell of dimensions a 10.006(6), b 14.240(8), c 18.368(6) Å, α 80.93(4), β 74.60(3), γ 89.23(5)°. The platinum atom has square planar geometry. The phosphorus atom of the chelated phosphine is trans to the methyl group. © 1990.