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  • Bioinorganic chemistry  (2)
  • Bicyclo[3.2.1]octanes, stereoselective syntheses of  (1)
  • 1
    ISSN: 0009-2940
    Keywords: Ring enlargement ; Phellandrene ; Carbonylation ; Bicyclo[3.2.1]octanes, stereoselective syntheses of ; Iron complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbonylating Ring Enlargement, 41). - Diastereoselective Syntheses of Bicyclo[3.2.l]oct-3-ene-2,8-diones by Double Carbonylation of (It)-(-)-α-PhellandreneIn order to clarify the stereochemistry of the carbonylating ring enlargement of cyclohexadiene complexes 1 to complexed seven-membered ring ketones 2 and the further carbonylation to bicyclo[3.2.1]oct-3-ene-2,8-diones 3 the exo and endo isomers of (R)-(-)-α-phellandrene complex 7 were synthesized in pure form and in various isomeric ratios and converted. The optically active ring-enlargement products 11 and 12 obtained therefrom, as well as the enantiomerically pure bicyclooctenes 20-22, implicate a stereospecific reaction course under retention of the configuration predetermined by the starting material 6 and its complexes 7. This was confirmed by an X-ray determination of the absolute configuration of exo-12. Thus, the method is suitable for the diastereoselective synthesis of bicyclo[3.2.1]oct-3-ene-2,8-diones 3 from 1,3-cyclohexadiene complexes 1.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Thiolato ligands ; Nickel complexes ; Hydrogenase models ; Bioinorganic chemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mononuclear Nickel Thiolate Complexes Containing Nickel Sites in Different Oxidation States: Molecular Definition of [Ni(SC6H4O)2]2- and [Ni(SC6H4O)2]Herrn Professor Dietrich Mootz zum 60. Geburtstag gewidmet.A solution of NiCl2·6 H2O in EtOH/H2O reacts with nBu3N and o1-mercaptophenol to form [nBu3NH]2[Ni(SC6H4O)2]·EtOH (2) containing the nickel(II) complex [Ni(SC6H4O)2]2- (1). The molecular structures of 1 and its oxidation product, [Ni(SC6H4O)2]- (3), have been determined by X-ray diffraction. With respect to the chemical as well as electrochemical properties of the nickel sites of various hydrogenases, 3 is the first relevant model complex of coordination number four whose structural properties have been determined in different oxidation states.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0570-0833
    Keywords: Thiols ; Bioinorganic chemistry ; Active centers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thiolates are presently a subject of great interest in the chemistry of complexes involving transition-metal elements and soft ligands. The manifold electronic and steric capabilities offered by the monodentate ligands RS⊖ and the bidentate chelate ligands ⊖SRS⊖ have been used to stabilize a broad spectrum of mononuclear, oligomeric, and polymeric complexes with new and remarkable structures and properties. Impetus has especially been provided by the synthesis of polynuclear cagelike homo- and heteroleptic metal-sulfur frameworks, which can often be regarded as “molecular fragments” of the structures of inorganic sulfides. Thiolates and mixed sulfide-thiolates of the late open- and closed-shell 3d metals (Fe, Co, Ni, Cu, Zn) and some of their homologues (Au, Cd, Hg), as well as of Mo, are of particular importance as model complexes for biologically important metal centers coordinated by sulfur. They have played an important role in increasing our understanding of the structure, bonding, and function of the reactive centers in ferredoxins, rubredoxins, nitrogenases, blue copper proteins, metallothioneins, and antiarthritic drugs.
    Additional Material: 41 Ill.
    Type of Medium: Electronic Resource
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