title: Mechanistic studies on the oxidation of ascorbic acid and hydroquinone by a {Mn4O6}4+ core in aqueous media.
abstract: Described in this work is the kinetics of oxidation of ascorbic acid and hydroquinone by a tetranuclear Mn(IV) oxidant, [Mn(4)(μ-O)(6)(bipy)(6)](4+) (1(4+), bipy =2,2(/)-bipyridine), in aqueous solution over a wide pH range 1.5-6.0. In particular, below pH 3.0, protonation on the oxo-bridge of 1(4+) results in the formation of [Mn(4)(μ-O)(5)(μ-OH)(bipy)(6)](5+) (1H(5+)) as an additional oxidant over 1(4+). Both ascorbic acid and ascorbate whereas only hydroquinone and none of its protolytic species were found to be reactive reducing agents in these reactions. Analysis of the rate data clearly established that the oxo-bridge protonated oxidant 1H(5+) is kinetically far more superior to 1(4+) in oxidizing ascorbic acid and hydroquinone. Rates of these reactions are substantially lowered in D(2)O-enriched media in comparison to that in H(2)O media. An initial one electron one proton transfer electroprotic rate step could be mechanistically conceived. DFT studies established that among the two sets of terminal and central Mn(IV) atoms in the tetranuclear oxidant, one of the two terminal Mn(IV) is reduced to Mn(III) at the rate step that we can intuitively predict considering the probable positive charge distribution on the Mn(IV) atoms.
authors.affiliation: Department of Chemistry, Jadavpur University, Kolkata 700 032, India.
authors.forename: Maharudra
authors.initials: M
authors.lastname: Chakraborty
authors.forename: N Jiten
authors.initials: NJ
authors.lastname: Singh
authors.forename: Pulak Chandra
authors.initials: PC
authors.lastname: Mandal
authors.forename: Suranjana
authors.initials: S
authors.lastname: Das
authors.forename: Subrata
authors.initials: S
authors.lastname: Mukhopadhyay
mesh_terms: D001205:Ascorbic Acid / Q000737:chemistry*; D006873:Hydroquinones / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D014867:Water / Q000737:chemistry
chemical_list: D006873:Hydroquinones; D009942:Organometallic Compounds; D014867:Water; D008345:Manganese; D001205:Ascorbic Acid; C031927:hydroquinone