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The primary aim of this thesis was to synthesise new hybrid-style cyclophosph(III)azane macrocycles composed to cyclophosph(III)azane units joined by difunctional linkers. The synthesis of the new macrocycles [{P(<i>μ</i>-N<i>^t</i>-N<i>^t</i>Bu)}₂{1,5-(NH)₂C₁₀H₆}]₃, [{P(<i>μ</i>-N<i>^t</i>Bu)}₂{1,4-(NH)₂C₆H₄}]₄, [{P(<i>μ</i>-N<i>^t</i>Bu)}₂{1,4-O₂C₆H₄}]₃ and [{P(<i>μ</i>-N<i>^t</i>Bu)}₂{(4,4’-NHC₆H₄)₂O}]₂ was achieved using [CIP(<i>μ</i>-N<i>^t</i>Bu)]₂ as the cyclophosph(III)azane precursor. These species include the largest cyclic oligomers known in this family of compounds. The synthesis of [{P(<i>μ</i>-NCy)}₂{1,5-O₂C₁₀H₆}]₃ showed that other cyclophosph(III)azane precursors can be used in these systems. Attempts to extend the same synthetic strategies to pyridyl-substituted cyclophosph(III)azanes, however, led to unexpected results which shed light on the reactivity of 2-pyridyl substituted cyclophosph(III)azanes. The new chain species [(C1{P(<i>μ</i>-N-4-Py)}₂)₂N-4-Py] represents a model intermediate in the formation of the previously reported bicyclic compound [Cl₂P₄(<i>μ</i>-N-2-Py)₅] and is a potential new precursor for the synthesis of macrocycles. The second aim of this thesis was to investigate the potential for forming 3D-cage structures using trimeric cyclophosph(III)azanes like [CIP(<i>μ</i>-Net)₃ as precursors. Extensive rearrangement of the P₃N₃ framework of the precursors and the tendency for oxidative hydrolysis caused major problems in this area. Finally, preliminary investigations of the coordination chemistry of the new macrocycles were carried out. The inclusion of solvent molecules <i>via</i> CH-arene interactions in the cavities of [{P(<i>μ</i>-N<i>^t</i>Bu)}₂{1,5-(NH)₂C₁₀H₆}]₃ and [{P(μ-NCy)}₂{1,5-O₂C₁₀H₆}]₃ in the solid state, along with the intra- and intermolecular hydrogen-bonding interactions observed in the solid-state structures of [{P(<i>μ</i>-N<i>^t</i>Bu)}₂{1,4-(NH)₂C₆H₄}] and [{P(<i>μ</i>-N<i>^t</i>Bu)}₂{(4,4’-NHC₆H₄)₂O}], highlight the potential of these macrocycles to act as hosts to a range of guest species.

This thesis is concerned with the synthesis and characterisation of electrospray-active phosphine ligands and their complexes, focusing on derivatives of proton sponges and bisphosphine monoxides (BPMOs). Phosphines containing Proton Sponge^® (1,8-<i>bis</i>(dimethylamino)naphthalene, 1a) have been synthesised via sequential bromination, lithiation and phosphination to give [{1,8-<i>bis</i>(dimethylamino)naphthalen-4-yl}diphenylphosphine] (12b), [{1,8-bis(dimethylamino)naphthalen-2-yl}diphenylphosphine] (12a) and [<i>bis</i>{1,8-<i>bis</i>(dimethylamino)naphthalen-2-yl}phenylphosphine] (13a). Complexes of 12a were shown to provide strong ESI-MS signals through the exclusive coordination of H⁺; [Mn(MeCp)(CO)₂(12a)] (14) and [W(CO)₅(12a)] (15) and iron carbonyl complexes of the form [Fe(CO)₄(P)] (P = PPh₃, P(<i>p</i>-C₆H₄OMe)₃, 12a) (16a-c) have been synthesised and characterised. The relative abilities of the phosphines ligands to act as electrospray handles within these complexes is discussed. The synthesis of a [Ru(η⁶-<i>p</i>-cymene)C1_x(12a)] species from [Ru(η⁶-<i>p</i>-cymene)Cl₂]₂ monitored and was shown to proceed through a long-lived detectable intermediate. 12a has been substituted onto PdCl₂(COD) and PtCl₂(COD) to form the [MC1₂(12a)₂] species. The interactions of 12a and 12a.HX with the Pd(0) complex [Pd(dba)₂], both in the absence and presence of 4-bromonitrobenzene, have been analysed by ESI-MS. The behaviour of both 12a and 12b has been investigated in a Suzuki (i.e. palladium-mediated) coupling reaction. The characteristics of BPMOs and the potential for these species to act as electrospray handles is described. Via <i>ortho</i>-lithiation of triphenylphosphine oxide with phenylithium and the reactions of the lithiated intermediate with electrophiles (TMSC1, D₂O, MeI, PR₂Cland PPhCl₂) a number of <i>ortho-</i>substituted products have been obtained. For reaction with PR₂Cl (where R = Ph, <i>i</i>Pr, Cy, Et) a range of BPMOs of the form Ph₂P(O)(<i>o</i>-C₆H₄)PR₂ have been synthesised. Reduction of 26a to give the bisphosphine product <i>o</i>-C₆H₄(PPh₂)₂ (dppbz) is also discussed. The reaction of [MC1₂COD] (M = Pt, Pd) with 26a formed the following complexes as mixtures; <i>cis</i>[PtCl₂(26a)₂] (31), [PtCl₂(26a)] (32), [PdCl₂(26a)] (33), [PdCl₂(26a)₂] (34) and [Pd₂Cl₄(26a)₂] (35). These were characterised by ESI-MS, ³¹P and ¹⁹⁵Pt NMR. An X-ray crystallographic structure of 32 was also determined. Synthesis of [Fe(CO)₄(26a)] (36) is described. The relevance of these results with a view to observance of metal complexes by ESI-MS is then discussed.

(1) An enantioselective organocatalytic ammonium enolate mediated intramolecular cyclopropanation reaction has been developed. Studies towards an asymmetric intramolecular epoxidation reaction as well as an organocatalytic cycloisomerisation reaction have also been undertaken. These processes are catalysed by cinchona alkaloid derivatives, of which a novel class, bearing an alkyl substituent in the 2-position of the quinoline moiety, has been developed. The intramolecular cyclopropanation reaction provided bicycle[4.1.0]alkanes in good yields (> 80%) and excellent e.e.’s (> 93%). The unoptimised e.e. for the intramolecular epoxidation was 40%, and e.e’s up to 95% were observed in the cycloisomerisation reaction. (Fig. 566397A) (2) Two novel concepts; trans-annular ring closure and “zip-up” strategy have been applied towards a synthesis of (-)-galanthamine. The racemic syntheses of advanced intermediates 212 and 226 were accomplished in few steps from commercially available starting materials.