1 results for Allen, Grant Richard

  • Laser pyrolysis of selected halogenated compounds with W(CO)6

    Allen, Grant Richard (2000)

    Doctoral thesis
    The University of Auckland Library

    The pyrolysis of selected halogenated compounds in the absence and presence of W(CO)6 has been investigated using infrared laser powered homogeneous pyrolysis (IR LPHP). The chemistry of these compounds in the absence of W(CO)6 is dominated by the themes of dehydrohalogenation (where available) and C–X bond homolysis (where X = halogen). The pyrolysis of W(CO)6 in the gas phase at moderate temperatures leads to unsaturated W(CO)x species; these prove to be very effective and selective abstractors of Cl and Br atoms from the selected halogenated compounds. The subsequent chemistry is dominated by the resulting organic radical moiety; observed end products are ascribed to disproportionation, combination, addition, rearrangement, abstraction and fragmentation of this species. The results pertaining to the pyrolysis of several of the oxygen-containing halogenated compounds in the presence of W(CO)6 suggest that unsaturated W(CO)x species are also effective abstractors of atomic oxygen. A number of the products observed can be attributed to intramolecular insertion of the resulting divalent carbon.

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