Synthesis and reactivity of new titanium hydrazido complexes

Thesis

This Thesis describes the synthesis and characterisation of titanium hydrazido(2-) and alkylidene hydrazido(2-) complexes and their reactivity towards unsaturated molecules. Exploration of the bonding in titanium hydrazido(2-) and alkylidene hydrazido(2-) complexes is performed through structural and computational studies.

Chapter 1 introduces current Group 4 hydrazido chemistry in comparison to Group 4 imido and mid/late metal hydrazido examples. Current Group 4 alkylidene hydrazido chemistry is also described.

Chapter 2 describes the synthesis, bonding and the novel reaction chemistry of titanium hydrazido(2-) half-sandwich complexes. Novel reactivity at the Ti=Nα bond is presented with the mechanisms of some of these transformations probed by Density Functional Theory (DFT) calculations.

Chapter 3 describes the novel reaction chemistry of Cp Ti{MeC(NiPr)2}(NNMe2) in comparison to its imido and diphenyl hydrazido analogues. Novel reactivity at both Ti=Nα and Nα–Nβ bonds is presented with the mechanisms of some of these transformations probed by Density Functional Theory (DFT) calculations.

Chapter 4 describes the synthesis and characterisation of a new titanium alkylidene hydrazido(2-) complex. The bonding of the alkylidene hydrazido(2-) ligand is explored through structural and computational studies. Novel reactivity at Ti=Nα and Nα-Nβ bonds is presented.

Chapter 5 presents full experimental procedures and characterising data for the new complexes reported.

Authors: Tiong, P

• Publication date: 2012
• DOI: 10.5287/ora-wxvrppg64
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Subjects: Inorganic chemistry