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  • Carbon dioxide fixation  (1)
  • Isomerizations, 2-propynyl-allenyl  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1077-1080 
    ISSN: 0009-2940
    Keywords: Molybdenum complexes ; Rearrangements, metal-induced, base-catalyzed ; Isomerizations, 2-propynyl-allenyl ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal-Induced and Base-Catalyzed 2-Propynyl-Allenyl Rearrangement in [(HC≡CCH2)(2,4,6-tBu3C6H2O)]P=MoCP(CO)2The synthesis and reactivity of [(HC≡CCH2)(2,4,6-tBu31-C6H2O)]P=MoCp(CO)2 (3) is described. [(HC≡CCH2)(R)]PCl (1) reacts with NaMoCp(CO)3 (2) to afford the s̰3,λ41-phosphanediyl compounds 3. With NEt3 a prototropic rearrangement of the 2-propynyl ligand of 3 to an allenyl group in [(H2C=C=CH)(R)]P=MoCp(CO)2 (5) is observed. However, with Cr(CO)5 · THF a metal-induced rearrangement of the 2-propynyl unit in 3 yields η3-{(2,4,6-tBu3C6H2O)[(CO)5Cr]PCHC=CH2}MoCp(CO)2 (7). Complex 7 contains a 1-phosphaallyl system, which is functionalized by an exocyclic CC double bond X-ray structure analyses of 3 and 7 are performed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Carbon dioxide fixation ; 1-Azadiene ligands ; Nickel(0) complexes ; Carboxylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organometallic CO2 Reservoires from Nickel(0)-1-Azadiene-Type Ligands and Their Reactivity in the Carboxylation of Acetophenone1-Azadiene-type ligands yield with nickel(0) binuclear organometallic compounds of the type [Ni(1-azadiene)n,]2 (n = 1, 2). The structures of the complexes 1 (n = 2, ligand A) and 3 (n = 1, ligand C) have been characterized by X-ray crystallography. 1 is unreactive towards CO2, 3 and similar compounds are able to react with CO2 to give metallacyclic carbamato complexes of Ni(II). In these compounds CO2 is activated and can carboxylate acetophenone to yield benzoylic acid upon protolysis. These reactions mimic biologic conversion reactions of CO2 into organic material by organometallics. - The addition of two moles of the (bpy)Ni(0)-fragment [from (bpy)Ni(COD)] to 3 gives the tetranuclear complex 6. The X-ray analysis of the monomeric model compound (bi-py)Ni(A) (11) shows that only the olefin part is coordinated. 6 and 11 can also react with CO2. Cu(I) complexes with 1-azadiene-type ligands are not reactive towards CO2.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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