Metal perfluoro-alkyl- and -aryl-thiolates. Part II. Molybdenum, tungsten, manganese, iron, and nickel derivatives

Photolytic reactions between bisulphides and carbonyl derivatives produce unstable Mn(CO)5SR and (π-C5H6)Ni(CO)SR (R = CF3 or C6F5) which dimerise through decarbonylation. (π-C5F5)Fe(CO)2SCF3 undergoes decarbonylation to isomers of [(π-C5H5)Fe(CO)SCF3]2 on photolysis. The structures of the isomers and factors affecting tendencies to dimerisation are discussed. [M(CO)4SCF3]2(M = Mo and W) are formed by photolysis of M(CO)6 and CF3SSCF3 using filtered radiation. Substitution of [Fe(CO)3SCF3]2 by triphenylphosphine to produce Fe2(CO)5(PPh3)(SCF3)2 and [Fe(CO)2(PPh3)SCF3]2 and by nitric oxide to produce [Fe(NO)2SCF3]2 is described.