Synthesis and coordination chemistry of multidentate phosphine ligands

The work presented herein is concerned with the design, synthesis and characterisation of novel phosphorus containing ligands and the metal complexes thereof. Chapter 1 will provide an introduction to the field and present an overview of recent developments in the literature. Chapter 2 deals with the development of a synthetic route towards triphosphine macrocycles. The synthesis of bis(2-(phosphino)ethyl)phosphines is presented and their coordination chemistry with first row transition metals (Cr, Fe, Ni, Cu) is described. The ability of these complexes to act as templates in the formation of macrocyclic ligands is assessed. Chapter 3 explores the synthesis of novel chiral multidentate phosphine ligands derived from glycidyl phosphine synthons. The reaction of diphenylglycidyl phosphine with P, N and S based nucleophiles results in the rapid construction of chiral heterodonor ligand frameworks. Preliminary studies of the reactivity of these ligands with metal centres will be presented. Chapter 4 investigates the synthesis of chiral-at-aluminium complexes based upon a novel γ-amino-β-hydroxyphosphine oxide ligand. Two discreet aluminium alkyl complexes were identified and the interconversion of these species was studied by spectroscopic and computational means. Chapter 5 concerns the coordination chemistry of bicyclic multidentate ER-NHCs with Pd(0), Pt(0) and Au(I) metal centres. The M(0) complexes display an unexpected proclivity towards the κ1-C coordination mode. This further informs the discussion of the factors controlling the variable coordination chemistry of such ligands in the design of novel catalytic systems