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  • 1
    ISSN: 0044-2313
    Keywords: Nickel ; Schiff base complexes ; synthesis ; crystal structure ; hydrogenase ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Green Bis-(2-iminoisopropyl-thiophenolato)nickel(II) and other Similar NiII ComplexesThe compounds [NiII(iitp)2] 1 (iitp = 2-iminoisopropyl-thiophenolate), [Ni2II(imptp)2] · 2 CH3OH 2, a dinuclear compound with an Ni—Ni distance of 276 pm, and [PPh4] · [NiII(imptp)(SCN)] 3 (imptp = 2-(2-iminopentane-4-on)-thiophenolate) have been prepared by the reaction of nickel(II)-acetate-tetrahydrate with 2-iminoisopropyl-thiophenole and 2-(2-iminopentane-4-on)-thiophenole in methanol, respectively. They have been characterized by single-crystal X-ray structure analysis and other physical methods. The redox behaviour of 1-3 has been studied in detail (chemically as well as by cyclovoltammetry and ESR spectroscopy). Particularly interesting are the electronic properties of 1 and its reduction with NaBH4 and the following reaction of the product with O2. The complexes are model compounds for some Ni-containing enzymes. For details of the crystal structure determination see “Inhaltsübersicht”.
    Notes: Die Verbindungen [NiII(iitp)2] 1 (iitp = 2-Iminoisopropyl-thiophenolat), [Ni2II(imptp)2] · 2 CH3OH 2, eine Zweikernverbindung mit einem Ni—Ni-Abstand von 276 pm und [PPh4][NiII(imptp)(SCN)] 3 (imptp = 2-(2-Iminopentan-4-on)-thiophenolat) wurden durch Umsetzung von Nickel(II)-acetat-tetrahydrat mit 2-Iminoisopropyl-thiophenol bzw. 2-(2-Iminopentan-4-on)-thiophenol in Methanol dargestellt und durch Einkristallstrukturanalyse und andere physikalische Methoden charakterisiert. Das Redoxverhalten der Verbindungen 1-3 wurde mittels elektrochemischer, chemischer und spektroskopischer Methoden untersucht. Bemerkenswert sind die elektronischen Eigenschaften der grünen Verbindung 1, sowie ihre Reduktion mit NaBH4 und die darauffolgende Umsetzung des Reaktionsproduktes mit O2. Die Verbindungen besitzen Modellcharakter für einige Ni-haltige Enzyme.1: C2/c, a = 1298,3(2); b = 695,7(1); c = 1958,7(3) pm; β = 103,92(1)°; V = 1717,4(5) · 106 pm3; R = 0,035 für 1230 unabhängige Reflexe (Fo 〉 4σ(Fo)), Z = 4.2: P1, a = 947,9(2); b = 1229,5(3); c = 1254,7(3) pm; α = 67,28(2), β = 74,63(2), γ = 81,18(2)°; V = 1298,4(5) · 106 pm3; R = 0,082 für 3655 unabhängige Reflexe (Fo 〉 4σ(Fo)), Z = 2.3: P21, a = 1119,3(2); b = 2389,7(4); c = 1245,8(2) pm; β = 102,52(1)°; V = 3253,0(9) · 106 pm3; R = 0,051 für 4218 unabhängige Reflexe (Fo 〉 4σ(Fo)), Z = 4.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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