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UBC Theses and Dissertations

EPR studies of aromatic nitrenes Dickinson, James Russell

Abstract

The studies presented in this thesis are in two areas. An investigation of aromatic nitrene molecules using EPR spectroscopy was undertaken. This revealed a general tendency for these molecules to exhibit two forms when trapped in a crystalline lattice. This is qualitatively interpreted as a perturbing effect of nitrogen evolved during generation from the azide. Single crystal experiments were made on 2,4,6-tribromophenyl nitrene, which exhibited an unusually large anisotropy in the zero field splitting, implying a bent structure. Temperature variation of several aromatic nitrene zero field splittings were made. The variation was interpreted as thermal averaging amongst states possessing different zero field parameters. The nature of these states however, could not be inferred. The variation is compared with similar studies. A computer program to least squares fit EPR angular data to a spin Hamiltonian has been written. This programme was used to obtain a description of the angularly dependent EPR data from an aromatic nitrene, and also for a radical species with a large hyperfine interaction.

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