title: Copper chalcogenide clusters stabilized with ferrocene-based diphosphine ligands.
abstract: The redox-active diphosphine ligand 1,1'-bis(diphenylphosphino)ferrocene (dppf) has been used to stabilize the copper(I) chalcogenide clusters [Cu12(μ4-S)6(μ-dppf)4] (1), [Cu8(μ4-Se)4(μ-dppf)3] (2), [Cu4(μ4-Te)(μ4-η(2)-Te2)(μ-dppf)2] (3), and [Cu12(μ5-Te)4(μ8-η(2)-Te2)2(μ-dppf)4] (4), prepared by the reaction of the copper(I) acetate coordination complex (dppf)CuOAc (5) with 0.5 equiv of E(SiMe3)2 (E = S, Se, Te). Single-crystal X-ray analyses of complexes 1-4 confirm the presence of {Cu(2x)E(x)} cores stabilized by dppf ligands on their surfaces, where the bidentate ligands adopt bridging coordination modes. The redox chemistry of cluster 1 was examined using cyclic voltammetry and compared to the electrochemistry of the free ligand dppf and the corresponding copper(I) acetate coordination complex 5. Cluster 1 shows the expected consecutive oxidations of the ferrocene moieties, Cu(I) centers, and phosphine of the dppf ligand.
authors.affiliation: Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A 5B7.
authors.forename: Chhatra B
authors.initials: CB
authors.lastname: Khadka
authors.forename: Bahareh Khalili
authors.initials: BK
authors.lastname: Najafabadi
authors.forename: Mahdi
authors.initials: M
authors.lastname: Hesari
authors.forename: Mark S
authors.initials: MS
authors.lastname: Workentin
authors.forename: John F
authors.initials: JF
authors.lastname: Corrigan