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1Author    Nicolai Burzlaff, Michael Hagel, WolfdieterA. SchenkRequires cookie*
 Title    Tuning the Steric and Electronic Properties of Chiral Rhenium Thiolate Complexes [1]  
 Abstract    Reaction of the complex [CpRe(NO)(CO)2]BF4 with triisopropylphosphine gives the chiral CO substitution product [CpRe(NO){P(/-Pr)3}(CO)]BF4. The corresponding triphenylphos-phite complex [CpRe(NO){P(OPh)3}(CO)]BF4 may be obtained by oxidative CO removal. Reduction of the remaining CO ligand with NaBH4 furnishes the corresponding methyl com­ plexes [CpRe(NO)(L)(CH3)]. The structure of [CpRe(NO){P(/-Pr)3}(CH3)] was determined: triclinic space group PI (No. 2), a = 8.442(4), b = 9.582(5), c -11.820(8) A, a = 81.81 (4), ß = 87.18(4), 7 = 63.87(5)°, Z = 2. Reaction of the methyl complexes with HBF4 in the presence of thiols gives, after chromatographic workup, the thiolate derivatives [CpRe(NO)(L)(SR)] (L = CO, P(OPh)3, P(/-Pr)3, R = CH2Ph, CH2(4-C6H4C1), CH2(4-C6H4OMe), CH3, C2H5). The structure of [CpRe(NO){P(/-Pr)3}(SCH3)] was determined: monoclinic space group P2i (No. 3), a = 7.0515(7), b = 17.3469(10), c = 7.9727(7) Ä, ß = 114.021(7)°, Z = 2. In both structures, a significant opening of the angle N-Re-X (X = C, S) suggests that antibonding interactions between orbitals of the ligand X and the second-highest MO of the [CpRe(NO)(L)] complex fragment are avoided. 
  Reference    Z. Naturforsch. 53b, 893—899 (1998); received May 5 1998 
  Published    1998 
  Keywords    Rhenium Complexes, Thiolate Ligands, Structure 
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 TEI-XML for    default:Reihe_B/53/ZNB-1998-53b-0893.pdf 
 Identifier    ZNB-1998-53b-0893 
 Volume    53 
2Author    Qianfeng Zhanga, Jinxi Chena, Maochun Hongb, Xinquan Xina, Hoong-Kun FuncRequires cookie*
 Title    Crystal and Molecular Structure of the Copper(I)-thiolate-selenide Complex [Ph4P][Cu(SeS2CNC4H8)(S2CN2C4H8)] with an Unusual Se-S Bond  
 Abstract    Reaction of a DMF solution of Cu(S^CNC4 H8) with [Ph4 P]2 [WSe4 ] affords [Ph4 P b[W Se4 -(CuS2CNC4H8)3 ] (1) and [Ph4P][Cu(SeS2 CNC4 H8)(S2 CN2 C4 H 8)] (2) in which a Se atom from the decomposition of the W Se4 2~ anion has reacted with the pyrrolidyldithiocarbamate (C4 H8dtc) ligand anion to form the new ligand anion SeSiC N C +H s'. Complex 2 crystallizes with four formula units in the monoclinic space group P2\/c in a cell of dimensions a = 10.5824(2), b = 18.7575(3), c = 18.3268(4) A and ß = 109.0980(10)°. 6055 independent reflections above background were measured with a diffractometer and the structure was re­ fined anisotropically to R =0.073. The anion contains a three-coordinated copper(I) atom. The C4 H8 dtcö ligand is bonded to the Cu+ cation in a terminal fashion, while SeS2 CNC4 H8~ chelates the Cu+ cation. The Se-S bond length is 2.231 (4) A. 
  Reference    Z. Naturforsch. 54b, 1313—1317 (1999); received April 4 1999 
  Published    1999 
  Keywords    Crystal Structure, Copper Complex, Selenium Complex, Thiolate Ligand 
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 TEI-XML for    default:Reihe_B/54/ZNB-1999-54b-1313.pdf 
 Identifier    ZNB-1999-54b-1313 
 Volume    54 
3Author    Berthold KerstingRequires cookie*
 Title    Synthesis and Structure of a Tetranuclear Nickel Complex of a 40-Membered Macrocyclic Octaamine-Tetrathiophenolate Ligand  
 Abstract    The syntheses and characterization of tetranuclear Ni complexes [(L2)Ni4][C104]4 (3) and [(L2)Ni4(NCS)4] (4) of a 40-membered macrocyclic octaamine-tetrathiophenolate ligand (L2)4-are described. Single-crystal X-ray structure analysis of 4 reveals well-separated molecules of the tetranuclear isothiocyanate complex [(L2) N i 4(NCS)4]. The four Ni" centers are arranged in binuclear [N2N i(^ 2-SR)2N iN 2(NCS)2] subunits containing distorted square-planar NiN 2S2 and distorted octahedral NiN 2S2(NCS)2 sites. The fact that the two isothiocyanate groups at the octahedral Ni site are in trans positions can be ascribed to the large ring size of the macrocycle. 
  Reference    Z. Naturforsch. 55b, 961—965 (2000); received July 7 2000 
  Published    2000 
  Keywords    Macrocyclic Ligands, Thiolate Ligand, Polynuclear Complexes 
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 TEI-XML for    default:Reihe_B/55/ZNB-2000-55b-0961.pdf 
 Identifier    ZNB-2000-55b-0961 
 Volume    55