University of Sussex
Williams,_Tara_N..pdf (60.33 MB)

Reactivity studies of electron poor titanium amides

Download (60.33 MB)
posted on 2023-06-07, 15:49 authored by Tara N Williams
Chapter One presents an overview of olefin polymerisation, which provides the context for the majority of the work described in later chapters. Both Ziegler-Natta and late transition metal systems are described. Chapter Two describes the synthesis and reactivity of trisamido titanium complexes with the diarylamido fragments derived from diphenylamine and di-p-tolylamine. These complexes have been thoroughly studied using NMR spectroscopy. This chapter also presents the syntheses of two rare examples of trisamido methyl complexes. In addition, an improved synthetic route to the cocatalyst, KB(C6F5)4 and the structures of [B(C6F5)C4H8O] and [Mg(C6F5)2(Et2O)(dioxane)] are described. Chapter Three describes the polymerisation activity of the catalysts derived from (R2N)3TiCl, (R2N)3TiMe, and [(R2N)3Ti]+ with the cocatalysts MAO, B(C6F5)3, and KB(C6F5)4. Data was recorded for each of the catalysts, and the consumption of propene over time was plotted. Rate constants were found for each of the polymerisation reactions. The mechanism for the polymerisation of each of these was also examined. Chapter Four presents the synthesis and reactivities of new trisamido complexes using 10,11-dihydro-dibenz(b,f )azepinyl, hereafter abbrievated as dda, as the amide fragment. Specifically, syntheses of (dda)3TiCl, (dda)3TiMe and (dda)3TiBH4 are described and their characterisation by NMR spectroscopy and X-ray crystallography is presented. The use of these complexes in synthetic approaches to (dda)3TiH are described. Initial steps in the characterisation of hydride transfer to CO2 from (dda)3TiH are also presented. Chapter Five presents details for the experimental work and Appendices are included, containing selected experimental data.


File Version

  • Published version



Department affiliated with

  • Chemistry Theses

Qualification level

  • doctoral

Qualification name

  • dphil


  • eng


University of Sussex

Full text available

  • Yes

Legacy Posted Date


Usage metrics

    University of Sussex (Theses)


    No categories selected