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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1105-1110 
    ISSN: 0044-2313
    Keywords: CO2 activation ; CO2 reduction ; reaction mechanism ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Activation of CO2 at Transition Metal Centres: The Route of the CO2 Reduction at Nikel(0) MoietiesA competing reaction in the catalytic cyclooligomerization of hex-3-yne and CO2 at the (TMED)Ni(0)-fragment (TMED = N,N,N′,N′-tetramethylethylendiamine) is the formation of carbon monoxide and (TMED)Ni(CO3). So it is possible to explain the generation of II (TMED)Ni(diethylmalicacidanhydride) and III (a nickel trimer with two (TMED)Ni(CO3) units). Both complexes are characterized by X-ray analysis. The reduction of CO2 to CO most likely proceeds via an intermediate in which two molecules of carbon dioxide are coupled head-to-tail to form a metallacycle. An ab initio scf geometry optimization supports the existence of such an intermediate.
    Notes: Konkurrenzreaktion bei der katalytischen Cyclooligomerisierung von Hex-3-in und CO2 am (TMED)Ni(0)-Fragment (TMED = N,N,N′,N′-tetramethylethylendiamin) ist die Entstehung von Kohlenmonoxid und (TMED)Ni(CO3). Damit kann die Bildung von II (TMED)Ni(Diethylmaleinsäureanhydrid) und III (trimer Nickelkomplex mit zwei (TMED)Ni(CO3)-Einheiten) erklärt werden. Beide Verbindungen wurden mittels Röntgenkristallstrukturanalyse charakterisiert. Der Ablauf der Reduktion des CO2 zu CO kann über ein Intermediate diskutiert werden, in dem zwei Kohlendioxidmoleküle unter Kopf-Schwanz-Verknüpfung zu einem Metallacyclus gekoppelt sind. Eine ab-initio-SCF Geometrieoptimierung stützt die Existenz eines solchen Intermediates.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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