Kinetics and mechanism of the oxidation of hydroxylamine by a {Mn(3)O(4)}(4+) core in aqueous acidic media

Abstract

[eng] In this work we report the kinetics of oxidation of hydroxylamine by a trinuclear Mn(IV) oxidant, [Mn3(μ-O)4(phen)4(H2O)2]4+ (1, phen = 1,10-phenanthroline), in aqueous solution over a pH range 2.0-4.0. The trinuclear Mn(IV) species (1) deprotonates in aqueous solution at physiological pH: 1 ⇌ 2 + H+; pK1 = 4.00 (± 0.15) at 25.0 °C, I = 1.0 (M) NaNO3. Both 1 and 2 are reactive oxidants reacting with the conjugate acid of hydroxylamine, viz.NH3OH+ where the deprotonated oxidant 2 reacts faster. This finding is in contrast to a common observation and belief that protonated oxidants react quicker than their deprotonated analogues. MnIV3 to MnII transition in the present reaction proceeds through the intervention of a spectrally detected mixed-valent MnIIIMnIV dimer that quickly collapses to MnII. The rate of the reaction was found to be lowered in D2O-enriched media in comparison to that in pure H2O media. An initial one electron one proton transfer to MnIV3 (electroprotic; 1e, 1H+) could be mechanistically conceived as the rate step. We also demonstrate by means of high level DFT studies that, among the two sets of Mn(IV) atoms in the trinuclear oxidant, the unique one that is coordinated with two phen ligands and two oxo-bridges is reduced to Mn(III) at the rate step. This is explained based on energetic and spin density calculations. Moreover, this result agrees with the charge distribution on the Mn atoms of the trinuclear complex.