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    A spectroscopic study of some organic free radicals

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    Author
    Greenaway, F. T.
    Date
    1972
    Permanent Link
    http://hdl.handle.net/10092/7915
    Thesis Discipline
    Chemistry
    Degree Grantor
    University of Canterbury
    Degree Level
    Doctoral
    Degree Name
    Doctor of Philosophy

    Several organic compounds which contain an unsaturated carbon-sulphur bond and amino or hydrazino groups have been x-irradiated at room temperature and at 105°K. Electron spin resonance has been used to identify the radical products of irradiation. The unsaturated carbon-sulphur bond is found to be resistant to irradiation damage, which generally occurs at another site in the molecule. In thiosemicarbazide and related compounds the major products of irradiation are nitrogen-centred π radicals and the structure of one such radical has been fully determined. In sodium diethydithiocarbamate, which has a delocalised Π-electron system the ionic products of irradiation are stabler and the radical cation has been characterised. Upon irradiation at room temperature however, the molecule undergoes structural deformation and the extended π-structure is destroyed. Mechanisms for the radiation damage which explain the observed products have been discussed.

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