Solvation, reactivity and spectroscopy of complexes of some first row transition metals
The work in this thesis is mainly concerned with the discussion of effect of solvation on the reaction kinetics of inorganic complexes. Rate constants for chemical reactions in various aqueous cosolvent systems have been measured and analysed. Crystal structure of several Fe (II) complexes are analysed from crystallographic data for possible structural parameters which might have effect on solvation. Solubility data, for a range of inorganic salts containing simple and complex ions, are reported for aqueous solutions and for solutions in aqueous cosolvent mixtures. Transfer chemical potentials for single ions in aqueous i-PrOH and t-BuOH solvent mixtures are determined using solubility data for salts in conjunction with TATB, tetraphenylarsonium tetraphenylboranate, assumption and are compared with those in corresponding aqueous methanol, ethanol and acetone solvent mixtures. Kinetic data are reported for reaction between [Fe (gmi)3]²+ and hydroxide ions at atmospheric and elevated pressures in above binary aqueous mixtures. Initial state and transition state analysis of reactivity trends for hydroxide attack on other Fe (II) diimine complexes in aqueous methanol solvent mixtures are reported. Dependence of visible absorption spectra on solvent has been examined for a number of Fe (II) and Fe (III) mixed ligand complexes. Preliminary redox study of the of Fe (II) and Fe (III) complexes is also reported.