Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferroceneligands

Abstract

The reaction of the unsymmetrical ligands 1-diphenylphosphino-1′-(phenylsulfanyl)ferrocene and 1-diphenylphosphino-1′-(phenylselenyl)ferrocene, Fc(EPh)PPh₂ (E = S, Se), with several group 11 metal derivatives leads to the synthesis of complexes of the type [MX{Fc(EPh)PPh₂}] (M = Au, X = Cl, C₆F₅; M = Ag, X = OTf), (OTf = trifluoromethanesulfonate), [M{Fc(EPh)PPh₂}₂]X (M = Au, X = ClO₄; M = Ag, X = OTf), [M(PPh₃){Fc(EPh)PPh₂}]OTf (M = Au, Ag), [Au₂{Fc(SPh)PPh₂}₂](ClO₄)₂, [Au(C₆F₅)₂{Fc(SePh)PPh₂}]ClO₄, [Au(C₆F₅)₃{Fc(EPh)PPh₂}], [Au₂(C₆F₅)₆{Fc(SePh)PPh₂}] or [Cu{Fc(EPh)PPh₂}₂]PF₆ (E = S, Se). In these complexes coordination depends upon the metal centre; with gold it takes place predominantly to the phosphorus atom and with silver and copper to both phosphorus and chalcogen atoms. The treatment of some of the gold complexes with other metal centres affords heterometallic derivatives that in some cases are in equilibrium with the homometallic derivatives. Several compounds have been characterized by X-ray diffraction, four pairs of homologous compounds, yet not a single pair is isotypic. In many of them a three dimensional network is formed through secondary bonds such as hydrogen bonds, Au⋯Cl or Au⋯Se interactions. The complex [Ag(OTf){Fc(SePh)PPh₂}] forms one-dimensional chains through trifluoromethanesulfonate bridging ligands.