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  • 1
    ISSN: 0044-2313
    Keywords: bimetallic Fe—Ni complexes ; CO2 fixation ; nickelalactones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organometallic Chemistry of Binuclear 1-Azadiene-Nickel(0) Complexes: Bimetallic Compounds with a Ni—Fe Bond by Addition of Pentacarbonyl-iron(0) and Nickelalactons by Ring Opening Reaction of Cyclic AnhydridesThe binuclear nickel(0) complexes 1-3, which contain as well bridging 1-azadienes ligands as five or six-membered (N∩N)-chelate rings react at -30°C with Fe(CO)5 to form the bimetallic compounds 4-6, containing a Ni—Fe bond and two carbonyl groups as bridging ligands. The coordination of the [(bpy)Ni(0)] fragment to the olefin part of the 1-azadiene chain in 6 leads to the formation of the trinuclear complex 7, which can storage CO2 at the peripheral position. Succinic acid anhydride or glutaric acid anhydrid undergo a ring opening reaction by reacting with 3 yield nickelalactones upon elimination of CO.
    Notes: Die binuclearen Nickel(0)-Komplexe 1-3, die verbrückende 1-Azadieneinheiten und N∩N-Chelatfünf- oder Sechsringe enthalten, reagieren bei -30°C mit Fe(CO)5 zu den Bimetallcarbonylverbindungen 4-6, die eine Ni—Fe-Bindung und 2 CO-Brückencarbonylliganden aufweisen. Koordination des (bipy)Ni(0)-Fragments an den Olefinteil der 1-Azadienkette 6 liefert den Dreikernkomplex 7, der an der Peripherie CO2 speichert. Bernsteinsäureanhydrid oder Glutarsäureanhydrid reagieren mit 3 unter Ringöffnung und CO-Eliminierung zu Nickelalactonen.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 101-106 
    ISSN: 0044-2313
    Keywords: Sodium phenoxide ; CO2 transfer ; carboxylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: CO2 Transfer by Metal Phenoxides: N-Methyl-ε-caprolactam/Sodium Phenoxide as a Selective Reagent for Carboxylation ReactionsCarboxylation reaction of aceton and other substrates with active C—H bonds can be carried out selectively by complexes of sodium phenoxide with N-methyl-ε-caprolactam („NMC“) and CO2. With aceton 3-keto-glutaric acid is formed in 85% yield upon hydrolysis. X-Ray structural analysis of the tetrameric [(NMC)Na(OPh)]4 shows that sodium- and oxygen ions of the phenoxide occupy the positions of a cubus. NMC acts as monodendate ligand, the oxygen atoms of the phenoxide are tridendate bridging ligands. The lithium compound has a similar structure. The complex solved in NMC takes up 0.5 mol CO2 per mol Natrium which at room temperature and normal pressure is transformed to aceton.
    Notes: Carboxylierungsreaktionen von Aceton und anderen Substraten mit aktiven C—H-Bindungen können selektiv mit Komplexen des Natriumphenolats mit N-Methyl-ε-caprolactam („NMC“) und CO2 durchgeführt werden. Mit Aceton entsteht in 85% Ausbeute nach Hydrolyse 3-Ketoglutarsäure. Die Röntgenstrukturanalyse des tetrameren Komplexes [(NMC)Na(OPh)]4 zeigt, daß Natrium- und Phenolatsauerstoffionen die Ecken eines Würfels besetzen.Na1 hat die Koordinationszahl 4. NMC fungiert als einzähliger Ligand, die Sauerstoffatome des Phenolats sind dreizählige Liganden. Die Lithiumverbindung hat eine vergleichbare Struktur. Der Komplex nimmt pro Mol Natriumion in NMC 0,5 Mol CO2 auf, das bei Raumtemperatur und Normaldruck auf Aceton übertragen wird.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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