Manganese(in) and its Hydroxo- and Chloro-complexes in Aqueous Perchloric Acid: Comparison with similar Transition-metal(m) Complexes

Abstract

At 25°C the formation constant of MnCl2+ is found by spectrophotometry to be 13.2 ± 0.9 dm3 mol–1 at ionic strength 3.26 mol dm–3; for MnCl+2 the value is 1.1 ± 0.7 dm3 mol–1. Increase in the number of chloride ions in complexes results in longer wavelengths for the corresponding absorption maxima. In the absence of chloride the hydrolysis constant of MnIII at ionic strength 5.6 mol dm–3 is found from voltammetry and potentiometry to be 1.05± 0.26 mol dm–3. Aged managanese(III) is found to be 15–25% polymeric, from both kinetic and e.m.f. measurements. Comparison of formation constants for halogeno- and hydroxo-complexes of M3+(first transition series) shows that a combination of charge-transfer, ligand-field and coulomb interactions underlies the observed sequences; the dipole moment of OH– is also a factor.