Synthesis and characterisation of 1-(diphenylphosphino)-1 '-(methylsulfanyl)ferrocene and a series of metal (Cu-I, Ag-I)-ferrocenylene complexes

A novel phosphorus/sulfur-substituted ferrocenylene ligand, 1-(diphenylphos phino)-1'-(methylsulfanyl)ferrocene has been synthesized by two routes and fully characterised. The co-ordination chemistry of this species and analog ous phosphorus/phosphorus- and sulfur/sulfur-substituted ferrocenylene liga nds, 1,1'-bis(diphenylphosphino)ferrocene, 1,1'-bis(methylsulfanyl)ferrocen e and 1,1'-bis(isopropylthio)ferrocene has been demonstrated by reaction wi th copper and silver tetrakis(acetonitrile) salts to form a series of metal -ferrocenylene complexes where the metal atom acts as a bridging group of t wo ring systems. Crystal structure determinations have been carried out on [Ag{(C5H4P(C6H5)(2))(2)Fe}(2)]BF4 and [Cu{(C5H4SCH3)(2)Fe}(2)]PF6 and illus trate that the former shows a distorted tetrahedral geometry around silver and a significant asymmetry in the geometries of the two pseudo six-membere d chelate rings and that the latter possesses S-4 symmetry with a pronounce d exo orientation of the four methyl groups.