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Abstract

Oxidative deselenation and desulphurisation at pentacovalent phosphorus, using a variety of chemical oxidising reagents and photochemically generated species has been investigated.

Chapter 1 provides a general introduction to the while chapters 2, 4 and 6 contain a discussion of oxidative deselenation at pentacovalent phosphorus with singlet oxygen, 1,2-dicarbonyl based initiators and a manganese III porphyrin in the presence of periodate ions and imidazole. Evidence for the involvement of singlet oxygen, in dye sensitised oxidative deselenation reactions, has been obtained from quenching studies and further inferred by examining the kinetic solvent isotope effect. The photooxidative deselenation reactions promoted by 1,2-dicarbonyl based initiators are thought to occur via the intermediacy of peroxy radicals. Possible mechanisms for these reactions have been postulated.

Chapters 3 and 5 report on the oxidative deselenation and desulphurisation at pentacovalent 3 phosphorus by number of photochemically generated species. These include a persulphoxide, excited N-oxides (or their photoproducts) and a carbonyl oxide.

In chapter 7 oxidative deselenation and desulphurisation at pentacovalent phosphorus, using a large number of chemical oxidising reagents, has been reported. Various mechanisms have been proposed.

Finally, chapter 8 describes the experimental procedure for the preparation of organophosphorus compounds, in addition to the details of the various oxidation reactions and methods for analysing the products of these reactions.

Publication Type:	Thesis (Doctoral)
Subjects:	Q Science > QD Chemistry
Departments:	School of Science & Technology > School of Science & Technology Doctoral Theses Doctoral Theses

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