Pyridinones and their complexes: Preparation and structure; solvation and reactivity in micelles.

Solvation trends for ligands and metal complexes formed by 3-hydroxy-4-pyridinones and 3-hydroxy-4-pyrones have been assessed through appropriate solubility measurements in water/alcohol mixtures, and from derived transfer chemical potentials. Solubility measurements were carried using uv/visible spectroscopy and atomic absorption. Transfer chemical potential trends are discussed in terms of the hydrophilic/lipophilic balance of ligand and complex periphery and nature of the solvent. Crystallographic data for three pyridinone ligands and two aluminium complexes are reported; the hydrogen-bonding and hydration found can be used to explain solution properties. A new method for the preparation of the ligands is reported along with the crystal structure of the first synthesised fluorinated pyridinone. Partition coefficients between bulk water and micelles have been determined in order to examine hydrophilic and hydrophobic effects of the periphery of pyridinone complexes. The amounts of water of crystallisation found in the crystal structures of the complexes are used in the explanation of reported results. Kinetics of ligand substitution of several pentacyanoferrate(II) complexes in micellar and reverse micellar systems have been determined. The results are discussed in terms of hydrophobic and electrostatic effects. Dependence of wavenumbers of maximum absorption for the lowest metal to ligand charge-transfer band of pentacyanoferrate(II) and iron(II)-diimine complexes has been reported in a series of solvents and solvent mixtures. Studies have also been carried out in micellar systems, for the pentacyanoferrate(II) complexes. These have been used to explain complex locations within micellar systems and kinetic trends within the surfactant systems studied.