Synthesis and properties of gold(III) pincer complexes with sulfur ligands

Currie, Lucy (2018) Synthesis and properties of gold(III) pincer complexes with sulfur ligands. Doctoral thesis, University of East Anglia.

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    Abstract

    This thesis investigates the synthesis of gold(III) pincer complexes and their functionalisation and reactivity with sulfur based ligands. The first chapter gives a brief introduction to gold chemistry, focusing on C^N^C gold(III) pincer complexes. The synthesis of these complexes and their subsequent functionalisation is described, emphasising their impact on our understanding of gold(III) chemistry.

    Chapter Two investigates the synthesis of a series of C^N^C gold(III) thiolate complexes. These complexes are photoluminescent and show either red or green emission. The emission properties are investigated in the solid state and solution. Analysis of crystal polymorphs with different emission properties show the potential for intermolecular interactions to affect the emission pathway. We identify two separate emission pathways resulting in the different emissions observed.

    Chapter Three explores the potential mechanisms of reductive elimination from C^N^C gold(III) complexes. Two different methodologies have been developed that trigger either C–S or C–C bond formation from a series of gold(III) complexes (chloride, thiolate, aryl and alkyl). The investigations are extended to further gold(III) heteroatom species and their reactivity is compared.

    Chapter Four investigates reactions of gold(III) complexes with two different transmetallating agents: organozinc halides and silyl boronic acids. Use of these transmetallating agents, to the best of our knowledge, is unexplored with gold(III) systems. Zinc aryl halides transmetallate Au–Cl and Au–S bonds affording gold(III) aryls in one step under mild conditions. The use of a silyl boronic acid in the transmetallation of Au–O bonds produces a gold(III) silyl complex.

    Chapter Five investigates the synthesis and anticancer properties of a series of C^N^C gold(III) NHC complexes. We investigate the potential influence of systemic alterations to both the pincer system and NHC upon the anticancer properties and DNA intercalation. In addition, the reactivity of these complexes with thiols is probed.

    Item Type: Thesis (Doctoral)
    Faculty \ School: Faculty of Science > School of Chemistry
    Depositing User: Gillian Aldus
    Date Deposited: 10 Jan 2019 13:03
    Last Modified: 10 Jan 2019 13:03
    URI: https://ueaeprints.uea.ac.uk/id/eprint/69536
    DOI:

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