Catalytic dechlorination of chloroalkenes by multimetallic cobaloximes: Synthesis, chemistry and catalysis

Arthur, Richard John 2010. Catalytic dechlorination of chloroalkenes by multimetallic cobaloximes: Synthesis, chemistry and catalysis. PhD Thesis, Cardiff University.

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Abstract

The work presented in this thesis is primarily concerned with the synthesis and applications of cobaloximes towards reductive dechlorination of organohalides, such as perchlorocthylene. The toxicity and relevance of these organohalides is discussed in chapter one, which also describes the current industrial methods for their removal from the environment. An insight into the mechanism of dechlorination of perchloroethylene has been offered in chapter three, which describes the mechanism of dechlorination of PCE. This reaction proceeds via electron transfer from the catalytic cobaloxime to the PCE for the removal of the first chloride, but the subsequent dechlorination steps proceed via organocobalt intermediates. The role of the axial ligands and the coordination chemistry' of the cobaloxime intermediate during reduction from Co(III) to Co(I) is then studied by means of a cross over experiment. Chapters four and five describe more complex, novel multimetallic cobaloximes, which have been designed and synthesised for their use as dechlorination catalysts. The structure and electrochemical behaviour of these multimetallic cobaloximes has been discussed and their catalytic ability towards dechlorination of PCE has been studied. The work in chapter four looks at cobaloximes with a u2-dicobaltcarbonyl bridged ligand, whilst chapter five describes a series of nitrogen heterocycle bridged dinuclear cobaloximes. As a result of the findings of chapter three, the final section of chapter five investigates the incorporation of the secondary metal centre into an equatorial ligand.

Item Type:	Thesis (PhD)
Status:	Unpublished
Schools:	Schools > Chemistry
Subjects:	Q Science > QD Chemistry
ISBN:	9781303218453
Date of First Compliant Deposit:	30 March 2016
Last Modified:	09 Jan 2018 19:45
URI:	https://orca.cardiff.ac.uk/id/eprint/55003

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