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Title: Synthetic and computational studies of group 3 and group 4 imido and hydrazido compounds
Author: Mellino, Simona
ISNI:       0000 0004 6501 1245
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2017
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This Thesis describes the synthesis and reactivity of titanium-nitrogen multiply bonded compounds. Mechanistic and bonding studies on titanium imido, hydrazido and borylimido complexes as well as on a novel scandium borylimide recently reported in our research group were described. Chapter 1 provides an introduction to Group 4 and Group 3 metal-nitrogen multiply bonded compounds including synthesis, bonding and reactivity of titanium imido, hydrazido, alkylidene hydrazido and borylimido complexes, (L)Ti=NR, (L)Ti=NNR2, (L)Ti=NNCR2 and (L)Ti=NBR2. Chapter 2 describes the reactions of the hydrazido compound Ti(N2 iPrNMe)(NNPh2)(py) with the Si - H and B - H bonds of silanes and boranes and with H2. The nature and mechanism of these reactions were investigated both computationally and experimentally. Chapter 3 explores a series of new reactions and unprecedented transformations of organic boranes and silanes with titanium half-sandwich compounds. In addition, detailed mechanistic work, using DFT calculations, was performed to understand the chemistry behind these reactions. Chapter 4 describes the bonding and reactivity of novel borylimido compounds. The systematic approach recently implemented in our research group to synthesise new titanium borylimido compounds, is described. A full computational study of the bonding of compounds with sandwich and half-sandwich structures is explained in detail. Chapter 5 explores the experimental attempts to isolate the first scandium borylimido complex performed in our group. DFT and QTAIM and detailed mechanistic study are presented. Chapter 6 contains experimental details, characterising data and DFT energies and coordinates of the optimized structures for the chemistry presented in Chapters Tw-Five.
Supervisor: Mountford, Philip Sponsor: Clarendon Fund
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available