Solvation of iron and chromium complexes in alcohol–water mixtures

Abstract

Solubilities are reported for the perchlorates of five iron(II)-diimine complexes in t-BuOH–H2O and one in MeOH–H2O mixtures, for three iron(III)-3-hydroxy-4-pyranonate and three iron(III)-3-hydroxy-4-pyridinonate complexes in MeOH–H2O and t-BuOH–H2O, and for two chromium(III)-3-hydroxy-4-pyranonate complexes in MeOH–H2O. Transfer chemical potentials are thence derived for the various iron(II), iron(III) and chromium(III) complexes, for transfer from H2O into the respective mixed solvents (at 298.2 K). These results are combined with values reported earlier for related complexes, and for other alcohol–H2O mixtures, to give an overall picture of solvation, expressed in the thermodynamic format of transfer chemical potentials, for iron(II)-diimine, iron(III)-3-hydroxy-4-pyridinonate and chromium(III)-3-hydroxy-4-pyranonate complexes in H2O-rich aqueous-alcohol mixtures. Some spectroscopic (1H-n.m.r.; i.r.) and kinetic (aquation rate constants at 298.2 K) data are reported for the chromium(III) complexes.