Synthetic and computational studies of group 3 and group 4 imido and hydrazido compounds

Thesis

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 ^iPrN^Me)(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.

Authors: Mellino, S

• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford