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Title: Adventures in low-valent germanium chemistry
Author: Mangan, Robert
ISNI:       0000 0004 8507 1536
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2020
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This thesis explores the use of boryl, terphenyl and amido ligands in a variety of interesting areas of low-valent germanium chemistry. In Chapter 1, a general introduction to the state of the art in this field is provided. The ligands that have proven pivotal in recent decades in germanium chemistry are introduced, and the developments that they have facilitated are then described. Finally, the field of germanium cations is introduced. In Chapter 2, the general methods deployed in this thesis' work are described; modified literature procedures for the syntheses of a variety of starting materials that were used in this work are also detailed. In Chapter 3, the synthesis of novel germylium-ylidenes is examined, utilising a strategy of chloride abstraction from chlorogermylenes substituted by a combination of N-heterocyclic carbene and anionic ligand. The structural characterisation of the first isolable germylium-ylidenes featuring boryl, terphenyl, primary amido, and borylamido ligands is reported, and the influence of these ligands on the structure of these compounds is discussed in detail. For instance, concerning terphenyl-substituted cations, the effect of subtle variation in ligand steric bulk is explored, in terms of changing the degree of aggregation, and leading to secondary interactions with the ligand peripheries. In Chapter 4, the reactivity of these germylium-ylidenes is then explored. The first activation of E-H bonds by isolable germylium-ylidenes is reported, as well as novel onward reactivity of some of the products as a result of their charge. For instance, oxidative addition of certain cations with ammonia leads to a subsequent elimination. Attempts towards the synthesis of multiple bonds is described, and the novel compounds this leads to discussed; for instance, reaction of a boryl-substituted cation with trimethylsilylazide leads to the formation of the first germylium azide. In Chapter 5, the synthesis of compounds featuring boryl-substituted germanium-transition metal bonds is investigated, and the first examples of such compounds for the cases of molybdenum, cobalt and iron are reported. In Chapter 6, conclusions are drawn from the work of this thesis, and suggestions for future work are made.
Supervisor: Aldridge, Simon Sponsor: Clarendon Fund
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Chemistry, Inorganic