Structures, kinetics, and solvation of pyranones, pyridinones and their complexes.

Pyran-4-one and pyridin-4-one ligands have been prepared, and used in the synthesis of a range of complexes of d- and f-block, and main group metal complexes, of oxidation states (II), (III), and (IV). The preparation and characterisation of pyranones and pyridinones is reported in Chapter 3. Crystallographic data for seven ligands are reported. A novel method is described for the synthesis of some ligands, of this type. Fluorescence characteristics for a number of ligands are discussed in terms of ligands, metal ion interactions, pH and solvent. Preparation and crystallographic characterisation of metal(II) and metal(III) complexes of pyranones and pyridin-4-ones are described. The structures of pyridinato complexes of lead(II) and cobalt(III), and of a pyranato complex of bismuth(III) reported, the hydrogen bonding and hydration, which may be of importance in explaining solvation, is described.. Solvation trends for transition and lanthanide group metals have been assessed in alcohol/water mixtures, Metal(IV) complexes of the type M(LL)2X2 have been prepared and characterised, where M = transition and main group metals. 1H, 13C and 119Sn NMR spectra are reported for a series of tin(IV) complexes. Crystallographic data are reported for three of these complexes. The in vitro cytotoxicity of four complexes of the type M(LL)2X2 is discussed. Rate laws and kinetic parameters are reported for substitution at M(LL)2X2. Reactivities are described in terms of nature of leaving group, incoming ligand, non-leaving ligand, central metal, and solvent. Activation volumes have been reported for the attack of thiocyanate on M(cp)2Cl2, M = Ti, V, and the attack of water at Ti(etmalt)2Cl2. Solvent and pressure effects on the metal to ligand charge-transfer band for titanium, vanadium and manganese thiocyanate complexes are reported.