Functional materials pervade an facets of science and technology. From enzymes to fluorophors, superconductors to multiferroics; they are integral components of devices and systems, both synthetic and biological. Yet in order to attain sufficient functionality, micro-and macroscopic control and compartmentalisation is essential during synthesis to ensure optimal product quality or systematic organisation of functional systems. While various common synthetic strategies yield appreciable product standards, many have inhibiting drawbacks which render the process impractical, unreliable or esoteric. By highlighting and understanding associated practical and mechanistic issues, a concerted effort can be made to devise alternative strategies which surpass those in terms of time, practicality, generality; energetic and financial costs; purity; and functional properties.

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This thesis concerns the investigation of a number of routes to the synthesis of novel heterometallic arrangements containing antimony. The initial aim was to investigate the potential ligand chemistry of the imido Sb(III) anions, [Sb(NR)<SUB>3</SUB>]<SUP>3-</SUP> - "the trianion". [Sb<SUB>2</SUB>(NR)<SUB>4</SUB>]<SUP>2-</SUP> - "the dianion", and [{(Me<SUB>2</SUB>N)Sb(<I>μ</I>-NR)<SUB>2</SUB>}<SUB>2</SUB>Sb]<SUP>-</SUP> - " monoanion", with a view to the incorporation of other metals into their p-block frameworks. Chapter 1 provides a brief overview of the general properties and organometallic chemistry of the p-block and then surveys the chemistry and reactivity of Group 13 and 14 complexes. It goes on to look at the chemistry of Group 15 and introduces the use of p-block dimethylamines [E(NMe<SUB>2</SUB>)<SUB>3</SUB> {E = Sb, Bi}] as the basis of the work in this thesis. Chapter 2 introduces the experimental techniques involved in the work and details the synthesis and analysis of the compounds made. Chapter 3 presents a study of the bonding and structure of different trianions with the dual aim of synthesising a range of multifunctional anion ligands. This investigation centres on the syntheses of three imido Sb(III) anions, [{Sb(NCy)<SUB>3</SUB>}<SUB>2</SUB>Li<SUB>6.</SUB>2HNMe<SUB>2</SUB>].2toluene (3a), [(Sb{N(2,4-dmp)}<SUB>3</SUB>)<SUB>2</SUB>Li<SUB>6.</SUB>2THF].2toluene (3b) and [{Sb(N<SUP>t</SUP>Bu)<SUB>3</SUB>}<SUB>2</SUB>Li<SUB>6</SUB>] (3c). It concludes that the Group 15 trianion units dominate these arrangements and that the [N<SUB>6</SUB>Li<SUB>6</SUB>] subunits perform an associative role. Chapter 4 details the further investigation of transmetallation reactions of the imido Sb(III) anions with a range of metal salts. The rigidity of these ligand systems and their application to the preparation of mixed-metal cages is illustrated by the syntheses and structures of the new cage complexes [Sb(NCy)<SUB>4</SUB>(HNCy)<SUB>2</SUB>]K.2toluene (4a), containing an early main group metal, [Sb<SUB>2</SUB>(NCy)<SUB>4</SUB>]<SUB>2</SUB>Ag<SUB>4</SUB> (4b), containing a transition metal, and [Sb(NCy)<SUB>3</SUB>]<SUB>2</SUB>Pb<SUB>3</SUB> (4c), containing a p-block metal. In Chapter 5 we see the extension of the imido Sb(III) anion work to the inclusion of phosphorus in the ligand framework. The stoichiometric assembly of the complex [Sb(PCy)<SUB>3</SUB>]<SUB>2</SUB>Li<SUB>6.</SUB>6HNMe<SUB>2.</SUB>2toluene (5a) creates a softer ligand set and a greater ligand bite than the imido congeners and has the potential to allow the stabilisation of low oxidation state transition metal centres. The discovery that thermolysis of 5a at 30°C gives the Zintl compound [Sb<SUB>7</SUB>Li<SUB>3.</SUB>6HNMe<SUB>2</SUB>] (5b) and, with TMEDA, [{(TMEDA)Li}<SUB>3</SUB>Sb<SUB>7</SUB>] (5c), provides an interesting study, as these complexes could be used in the manufacture of photodiodes.

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