Cationic carbonylnitrosyl complexes of molybdenum and tungsten

Abstract

The complexes [M(CO)4(diphos)][M = Mo and W; diphos = 1,2-bis(diphenylphosphino)ethane, Ph2PCH2CH2PPh2] and NOPF6 react in methanol–toluene to afford [M (CO)3(NO)(diphos)]PF6 which, in turn, react with halides, X–, and dithiocarbamate salts, Na[S2CNR2](R = Me and Et), to give [M(CO)2(NO)(diphos)X] and [M(CO)(NO)(diphos)(S2CNR2)] respectively. With phosphine ligands, L, [Mo(CO)3(NO)(diphos)]PF6 reacts in chloroform to yield [M(CO)(NO)(diphos)(L)Cl][L = PPh3, P(OPh)3, P(OMe)3, and diphos] and in acetone to give [Mo(CO)2(NO)(diphos)(PPh3)]2(PF6)2′2acetone and [Mo(CO)(NO)(diphos)2]PF6. When heated under reflux in chloroform the complex [Mo(CO)3(NO)(diphos)]PF6 is decarbonylated to yield [Mo(NO)-(diphos)Cl2]n and other polynuclear nitrosyl species.