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Synthetic and theoretical investigations involving compounds containing low oxidation state main group elements

Green, Shaun Peter 2008. Synthetic and theoretical investigations involving compounds containing low oxidation state main group elements. PhD Thesis, Cardiff University.

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Abstract

The work presented in this thesis is concerned with synthetic and theoretical investigations involving compounds containing low oxidation state elements from across the main group. Chapter 1 provides a general introduction to low oxidation state group 13 chemistry, with an emphasis on the preparation and reactivity of group 13 metal(I) halides and alkyls. Additionally, the jV-heterocyclic carbene class of ligand and its group 13 valence isoelectronic analogues are discussed. Chapter 2 details the use of the low oxidation state gallium halide species, 'Gal9, as a new reducing agent in organic synthesis, predominantly in the reactivity towards a-functionalised ketones. Isolation of inorganic intermediates aided in the proposal of reaction mechanisms, including the first structural characterisation of a gallium enediolato complex. Chapter 3 investigates the dissolution of the indium(I) halides, which in the case of the bromide and iodide, afforded the first structurally characterised molecular indium(I) halide complex and neutral indium subhalide complex, respectively. For the first time, the study also established that InBr can be crystallised from an organic solvent. Chapter 4 explores the synthesis, electronic structure and reactivity of unprecedented magnesium(I) and related magnesium(II) hydride complexes. The magnesium(I) complexes contain the first structurally characterised Mg-Mg bonds while the magnesium(II) hydrides are the first structurally characterised examples of neutral complexes of the type {L Mg(//- in - 1 or 2). Chapter 5 pertains to theoretical studies involving low oxidation state group 14 and 15 amidinate and guanidinate complexes, based on experimental investigations that led to several digermynes and diarsenes. In part, the study deals with multiple bonding, or lack thereof, between the corresponding metal centres. Chapter 6 describes the electronic structure of novel main group and transition metal complexes bearing Group 13 heterocyclic ligands, examples of which illustrate the first structurally characterised Ga-Sn bond and shortest Ga-Pt bond.

Item Type: Thesis (PhD)
Status: Unpublished
Schools: Chemistry
Subjects: Q Science > QD Chemistry
ISBN: 9781303214967
Date of First Compliant Deposit: 30 March 2016
Last Modified: 12 Feb 2016 23:13
URI: http://orca-mwe.cf.ac.uk/id/eprint/54872

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