Metal perfluoroalkane- and perfluoroarene-thiolates. Part V. The reactions of tricarbonyl(π-cyclopentadienyl)-molybdenum and -tungsten thiolates and acetylenes

Abstract

The thiolates [(η⁵-C₅H₅)M(CO)₃SR_F](M = Mo or W; RF = CF₃ or C₆F₅) react with acetylenes, RCCR (R = CF₃, Me, or Ph) to give the formally electron-deficient π-acetylene complexes [(η⁵-C₅H₅)M(CO)(RC₂R)SR_F]. The bonding and isomerism in these complexes at low temperatures is discussed. On oxidation [(η-C₅H₅)MoO(CF₃C₂CF₃)SC₆F₅] can be isolated. Trifluoropropyne reacts with the thiolates to give the acetylene complex [(η⁵-C₅H₅)Mo(CO)(CF₃C₂H)SC₆F₅] and cyclopentadienone complexes [(η⁵-C₅H₅)Mo(CO){(CF₃C₂H)₂CO}SCF₃] and [{(η⁵-C₅H₅)[(CF₃C₂H)₂CO]SCF₃}₂].