Synthesis and characterisation of 1-(diphenylphosphino)-1′-(methylsulfanyl)ferrocene and a series of metal (CuI, AgI)–ferrocenylene complexes

Abstract

A novel phosphorus/sulfur-substituted ferrocenylene ligand, 1-(diphenylphosphino)-1′-(methylsulfanyl)ferrocene has been synthesized by two routes and fully characterised. The co-ordination chemistry of this species and analogous phosphorus/phosphorus- and sulfur/sulfur-substituted ferrocenylene ligands, 1,1′-bis(diphenylphosphino)ferrocene, 1,1′-bis(methylsulfanyl)ferrocene and 1,1′-bis(isopropylthio)ferrocene has been demonstrated by reaction with copper and silver tetrakis(acetonitrile) salts to form a series of metal–ferrocenylene complexes where the metal atom acts as a bridging group of two ring systems. Crystal structure determinations have been carried out on [Ag{(C₅H₄P(C₆H₅)₂)₂Fe}₂]BF₄ and [Cu{(C₅H₄SCH₃)₂Fe}₂]PF₆ and illustrate that the former shows a distorted tetrahedral geometry around silver and a significant asymmetry in the geometries of the two pseudo six-membered chelate rings and that the latter possesses S₄ symmetry with a pronounced exo orientation of the four methyl groups.