Synthesis, deracemisation, photochemistry and crystallisation studies in organic, organometallic and coordination chemistry directed towards circularly polarised light and chiral amplification.

Casadesus, Meritxell 2007. Synthesis, deracemisation, photochemistry and crystallisation studies in organic, organometallic and coordination chemistry directed towards circularly polarised light and chiral amplification. PhD Thesis, Cardiff University.

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Abstract

The work described in this thesis is based around attempts to find a system that could use the intrinsic chirality of circularly polarised light (CPL) to generate a small enantiomeric excess in photochemical reactions and couple it with crystallisation-induced chiral amplification to obtain a high enantiomeric excess. This type of system could provide a possible model for the origins of homochiral life on Earth. In order to study this possibility, synthetic and photochemical work has been carried out in the organic, inorganic and organometallic fields. The synthesis of a new family of axially chiral benzylidenes and their enantiomeric resolution has been developed and the influence of CPL in the racemisation of the double bond has been studied. The synthesis of a new family of Werner-type cobalt coordination complexes has been developed and their crystal packing studied, with special emphasis on the role of hydrogen bonding towards the crystal packing. The effect of CPL in the crystallisation pattern has also been investigated, along with a reinvestigation of polymorphism in a previously reported complex. Finally, the synthesis of a new family of thioalkynyl derivatives has been developed with the subsequent products coordinated to dicobalt octacarbonyl. The displacement of a CO group and further coordination of the pendant sulphide to cobalt has been studied chemically and spectroscopically and the effect of CPL on the photochemistry of Co2(CO)Fe-alkyne compounds has been investigated. A new dechlorination reaction discovered during these studies is also discussed in this thesis.

Item Type:	Thesis (PhD)
Status:	Unpublished
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
ISBN:	9781303181764
Date of First Compliant Deposit:	30 March 2016
Last Modified:	09 Jan 2018 22:54
URI:	https://orca.cardiff.ac.uk/id/eprint/55653

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