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.