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

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, H NMR, P NMR and electronic absorption spectroscopy. The crystal structures of dichlorido[1-diphenylphosphinoyl-1'-(di-tert-butylphosphanyl)ferrocene-κO,P]cadmium(II), [CdCl{(CHOP)(CHP)Fe}] or CdCl(κP,O-dppOdtbpf) (1), bis[μ-(tert-butyl)(1'-diphenylphosphinoylferrocen-1-yl)phosphinato-κO,O':O'']bis[chloridozinc(II)], [Zn{(CHOP)(CHOP)Fe}Cl] or [ZnOCl{κO,O'-PhPOFcPO(t-Bu)}] (2), 1,1'-bis(di-tert-butylthiophosphinoyl)ferrocene, [Fe(CHPS)] or dtbpfS (3), and [1,1'-bis(dicyclohexylphosphanyl)ferrocene-κP,P'][chlorido/cyanido(0.25/1.75)]zinc(II), [Zn(CN)Cl{(CHP)Fe}] or Zn(CN)(κ-dcpf) (4), were determined crystallographically. Compound 1 has tetrahedral geometry in which the Cd centre is coordinated by one dppOdtbpf ligand in a κ-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 Zn atom adopts a tetrahedral geometry by coordinating to the 1,1'-bis(dicyclohexylphosphanyl)ferrocene ligand in a κ-manner and to two cyanide ligands.