Transition-metal complexes of group 12 with 1,1′-bis(phosphanyl)ferrocene ligands

Abstract

The syntheses of four new cadmium and zinc complexes with 1,1′-bis(phosphanyl)ferrocene ligands and their phosphine chalcogenide derivatives are reported. The complexes were characterized by elemental analyses and IR, 1H NMR, 31P NMR and electronic absorption spectroscopy. The crystal structures of dichlorido[1-diphenylphosphinoyl-1′-(di-tert-butylphosphanyl)ferrocene-κ2 O,P]cadmium(II), [CdCl2{(C17H14OP)(C13H22P)Fe}] or CdCl2(κ2 P,O-dppOdtbpf) (1), bis[μ-(tert-butyl)(1′-diphenylphosphinoylferrocen-1-yl)phosphinato-κ3 O,O′:O′′]bis[chloridozinc(II)], [Zn2{(C9H13O2P)(C17H14OP)Fe}2Cl2] or [ZnOCl{κ2 O,O′-Ph2POFcPO2(t-Bu)}]2 (2), 1,1′-bis(di-tert-butylthiophosphinoyl)ferrocene, [Fe(C13H22PS)2] or dtbpfS2 (3), and [1,1′-bis(dicyclohexylphosphanyl)ferrocene-κ2 P,P′][chlorido/cyanido(0.25/1.75)]zinc(II), [Zn(CN)1.75Cl0.25{(C17H26P)2Fe}] or Zn(CN)2(κ2-dcpf) (4), were determined crystallographically. Compound 1 has tetrahedral geometry in which the CdII centre is coordinated by one dppOdtbpf ligand in a κ2-manner and by two Cl atoms, while compound 2 displays a centrosymmetric dimeric unit in which two oxide atoms bridge the two Zn atoms to generate an eight-membered ring. Compound 3 revealed a sandwich structure with both phosphane groups sulfurized. In compound 4, the ZnII atom adopts a tetrahedral geometry by coordinating to the 1,1′-bis(dicyclohexylphosphanyl)ferrocene ligand in a κ2-manner and to two cyanide ligands.