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1996 (1)
1Author    Martin Köckerling, Gerald HenkelRequires cookie*
 Title    Nickelkomplexe  
 Abstract    mit Thioether-Chelatliganden: Elektrochemische Eigenschaften und Kristallstrukturen von [Ni(MeSCH2CH2SMe)2 (NCS)2], [Ni(EtSCH2CH2SEt)2(NCS)2] und [Ni(MeSCH2CH2SMe)2Br2] Nickel Complexes with Chelating Thioether Ligands: Electrochemical Properties and Crystal Structures of [Ni(MeSCH2CH2SMe)2(NCS)2], [Ni(EtSCH2CH,SEt)2(NCS)2] and [Ni(MeSCH2CH2SMe)2Br2] interest in nickel complexes with sulfur donor ligands as models for the active sites of nickel-containing hydrogenases has prompted us to investigate the structural and elec­ trochemical behaviour of nickel complexes with bifunctional thioether ligands. Crystals of [Ni(MeSCH,CH,SMe),(NCS),] (1) and [Ni(EtSCH2CH,SEt)2(NCS)2], (2) are triclinic, space group Pi, Z = 1, 1: a = 7.293(3) A, b = 7.567(3) A, c = 8.784(3) A, a = 72.81(3)°, ß = 78.41(3)°, 7 = 85.14(3)°; 2: a = 8.611(1) A, b = 8.101(1) Ä, c = 9.163(1) ßrbÄ, a = 66.54(1)°, ß = 76.19(1)°, 7 = 67.88(1)ßrb°. [Ni(MeSCH2CH2SMe^Br2] (3) crystallizes in the mono­ clinic space group P2,/n, a = 6.757(2) A, b = 7.881(2) A, c = 14.674(4) Ä, ß = 94.05(2)°, Z = 2. In crystals of 1, 2 and 3 mononuclear neutral complex molecules are observed which have pseudo-octahedral rran5-NiS4L2 coordination sites. The cyclovoltammograms of 1 and 3 in MeCN (Ag/AgCl/KCl, 3 mol/1) show only irreversible oxidation waves at +837 mV for 1 and +846 mV for 3, respectively, which are characteristic features of NCSe and Bre ions. In addition, a reduction wave at +393 mV is observed in 3. No redox response is found in the potential region between -700 and +100 mV which is used by the NiFe hydrogenase enzymes. 
  Reference    Z. Naturforsch. 51b, 178—186 (1996); eingegangen am 18. Juli 1995 
  Published    1996 
  Keywords    Nickel-Sulfur Complexes, Thioether Ligands, Crystal Structure, Electrochemistry, Bioinorganic Chemistry Current 
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 TEI-XML for    default:Reihe_B/51/ZNB-1996-51b-0178.pdf 
 Identifier    ZNB-1996-51b-0178 
 Volume    51