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  • Tetracobalt cluster  (1)
  • sulfido-bridged clusters  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Synthesis, redox chemistry, and X-ray structure of the mixed-metal cluster Fe2(CO)6(μ3-S)2Ni(dppf) (1999)
    Springer
    Journal of chemical crystallography 29 (1999), S. 871-876 
    Details
    ISSN: 1572-8854
    Keywords: mixed-metal clusters ; sulfido-bridged clusters ; electrochemistry ; extended Hückel MO calculations ; x-ray structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The reaction between the dianion [Fe2(CO)6(μ2-S)2]2− and NiCl2(dppf) occurs readily at room temperature to give the mixed-metal cluster Fe2(CO)6(μ3-S)2Ni(dppf) in moderate yield. Fe2(CO)6(μ3-S)2Ni(dppf) was isolated by preparative chromatography and its solid-state structure established by X-ray diffraction analysis. Fe2(CO)6(μ3-S)2Ni(dppf) crystallizes in the monoclinic space group C2/c, a = 20.320(6), b = 13.114(2), c = 15.622(2) Å, β = 110.25(2)°, V = 3905.4(11) Å3, Z = 4, and d calc = 1.630 g/cm.3 The X-ray structure of Fe2(CO)6(μ3-S)2Ni(dppf) exhibits an Fe2S2Ni arachno polyhedral core, with the pendant dppf ligand attached to an essentially square planar Ni center. The redox chemistry of Fe2(CO)6(μ3-S)2Ni(dppf) was investigated by cyclic voltammetry which showed a reversible, one-electron oxidation localized on the Fe2S2 core along with an irreversible, one-electron reduction that is antibonding with respect to the Fe—Fe and Fe—S bonds. The electrochemical assignments were confirmed by carrying out extended Hückel MO calculations on the model cluster Fe2(CO)6(μ3-S)2Ni(H4-dppf).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009565726187
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  • 2
    Electronic Resource
    Electronic Resource
    PhPMe2 ligand substitution in the tetracobalt cluster Co4(CO)10(μ4-PPh)2: X-ray diffraction structure of Co4(CO)8(PPhMe2)2(μ4-PPh)2 (1996)
    Springer
    Journal of chemical crystallography 26 (1996), S. 75-79 
    Details
    ISSN: 1572-8854
    Keywords: Tetracobalt cluster ; phosphine ligand ; regiochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The thermal substitution chemistry of the tetracobalt cluster Co4(CO)10(μ4-PPh)2 with the phosphine ligand PhPMe2 (2.5 equiv) has been explored and found to afford the bis(phosphine)-substituted cluster Co4(CO)8(PPhMe2)2(μ4-PPh)2 as the major reaction product. The regiochemistry and stereoselectivity exhibited by the two phosphine ligands in Co4(CO)8(PPhMe2)2(μ4-PPh)2 have been unambiguously established by X-diffraction analysis as having a 1,3-cis orientation. Co4(CO)8(PPhMe2)2(μ4-PPh)2 crystallizes in the monoclinic space group P21/n,a=10.314(1) Å,b=18.051(3) Å,c=21.313(2) Å, β=90.10(1)°,V=3968.0(8) Å3,Z=4,d calc=1.590 g cm−3;R=0.051,R w=0.042 for 4987 observed reflections withI〉3σ(I). Generalizations concerning the stereochemical disposition of two P-ligands about the Co4(CO)8P2(μ4-PPh)2 (where P=phosphine or phosphite) polyhedron are discussed with respect to the cone angle of the P-ligand and its steric interactions with the capping phenylphosphinidene group.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02018701
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