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The work presented in this thesis is divided into two parts, both of which investigate the chemistry of main group elements supported by N,N'-donor ligands.  Part 1 investigates the use of Mg(mesC{NCy}₂)(N{SiMe₃}₂)(THF) (mes = 2,4,6- Me₃C₆H₃, Cy = C₆H₁₁) as a pre-catalyst for the coupling of terminal acetylenes to carbodiimides. A catalytic cycle for the reaction is proposed, based on a series of stoichiometric reactions. Ligand redistribution via Schlenk equilibria is a prominent feature of the proposed catalytic cycle. The scope of catalysis was also investigated, indicating a strong dependence on the sterics and electronics of both the carbodiimide and the terminal acetylene. Investigation of other magnesium species identified other pathways into the catalytic cycle.  Part 2 explores the derivitisation of Bi(Me₂Si{NAr})Cl (Ar = 2,6-i-Pr₂C₆H₃) to form a number of novel bismuth(III) species of the general formula Bi(Me₂Si{NAr})X (X = alkyl, aryl, amide, aryloxide, phosphide). In addition, a number of cationic bismuth species have been isolated from the reaction of Bi(Me₂Si{NAr})Cl with ECl₃ (E = Al, Ga). Preliminary investigations reveal that the amide and aryloxide derivatives are active as initiators for the ring-opening polymerisation of lactide and ε-caprolactone. A number of bismuth(III) compounds bearing the related di(amido)ether ligands [O(Me₂Si{NAr})₂]²⁻ have also been synthesised.

I. Magnesium Promoted Coupling of Carbodiimides and Terminal Acetylenes, II. Bismuth Compounds Supported by Di(amido) Chelating Ligands