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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 10 (1971), S. 776-786 
    ISSN: 0570-0833
    Keywords: Polymerization ; Polyethylene ; Vanadium ; Chromium ; Catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the present progress report literature data concerning homogeneous catalyst systems based on vanadium and chromium are reviewed and complemented by a combined study of the magnetic properties and the polymerization activity of such systems. The results show that vanadium forms active species as V (III) and as V (II), but chromium only as Cr (II); models are suggested for the polymerization process.  -  A comparison with heterogeneous systems (Phillips catalyst) allows the establishment of some general principles concerning the activity of the catalyst and the properties of the polymers.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0570-0833
    Keywords: Ziegler-Natta catalysts ; Catalysis ; Polymerization ; Polyethylene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cp2TiCl2 and Cp2TiEtCl (Cp = cyclopentadienyl, Et = ethyl), in combination with aluminum alkyls, have been studied as model catalyst systems for the polymerization of ethylene in toluene. The activity of these systems resides in the presence of a complex molecule involving an alkylated Ti(IV) and an alkylated Al species, linked together by chlorine bridge bonds. The environment of the Ti is of octahedral symmetry with one vacant site available for the coordination of ethylene. The bridged Al-alkyl causes a destabilization of the Ti-alkyl bond (“trans effect”), thus rendering it active for polymerization. The reduction Ti(IV) → Ti(III), inevitable in these systems, involves the irreversible change from octahedral to tetrahedral symmetry with loss of the catalytic activity. Polymerization and reduction are supposed to occur at the same catalyst site. Magnetic methods (susceptibility and EPR) as well as the kinetics of polymerization were used in the investigation of these catalyst systems.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 8 (1969), S. 650-659 
    ISSN: 0570-0833
    Keywords: Activation ; Nitrogen fixation ; Nitrogen fixation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several transition metal complexes that can absorb nitrogen from the gas phase are now known. Some of the N2-metal complexes are stable enough to be isolated and their structure elucidated, the N2 molecule remaining chemically inert. In other cases reduction to N3- is possible, but the structure of the reactive intermediate N2-metal complex can be approached only by mechanistic studies. In the stable complexes the nitrogen is bound via a lone pair of electrons in the direction of the molecular axis (“end-on”), in the reducible complexes possibly “edge-on”.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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