title: Hydrogen-atom abstraction reactions by manganese(V)- and manganese(IV)-oxo porphyrin complexes in aqueous solution.
abstract: High-valent manganese(IV or V)-oxo porphyrins are considered as reactive intermediates in the oxidation of organic substrates by manganese porphyrin catalysts. We have generated Mn(V)- and Mn(IV)-oxo porphyrins in basic aqueous solution and investigated their reactivities in C-H bond activation of hydrocarbons. We now report that Mn(V)- and Mn(IV)-oxo porphyrins are capable of activating C-H bonds of alkylaromatics, with the reactivity order of Mn(V)-oxo>Mn(IV)-oxo; the reactivity of a Mn(V)-oxo complex is 150 times greater than that of a Mn(IV)-oxo complex in the oxidation of xanthene. The C-H bond activation of alkylaromatics by the Mn(V)- and Mn(IV)-oxo porphyrins is proposed to occur through a hydrogen-atom abstraction, based on the observations of a good linear correlation between the reaction rates and the C-H bond dissociation energy (BDE) of substrates and high kinetic isotope effect (KIE) values in the oxidation of xanthene and dihydroanthracene (DHA). We have demonstrated that the disproportionation of Mn(IV)-oxo porphyrins to Mn(V)-oxo and Mn(III) porphyrins is not a feasible pathway in basic aqueous solution and that Mn(IV)-oxo porphyrins are able to abstract hydrogen atoms from alkylaromatics. The C-H bond activation of alkylaromatics by Mn(V)- and Mn(IV)-oxo species proceeds through a one-electron process, in which a Mn(IV)-oxo porphyrin is formed as a product in the C-H bond activation by a Mn(V)-oxo porphyrin, followed by a further reaction of the Mn(IV)-oxo porphyrin with substrates that results in the formation of a Mn(III) porphyrin complex. This result is in contrast to the oxidation of sulfides by the Mn(V)-oxo porphyrin, in which the oxidation of thioanisole by the Mn(V)-oxo complex produces the starting Mn(III) porphyrin and thioanisole oxide. This result indicates that the oxidation of sulfides by the Mn(V)-oxo species occurs by means of a two-electron oxidation process. In contrast, a Mn(IV)-oxo porphyrin complex is not capable of oxidizing sulfides due to a low oxidizing power in basic aqueous solution.
authors.affiliation: Department of Chemistry and Nano Science, Centre for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea.
authors.forename: Chellaiah
authors.initials: C
authors.lastname: Arunkumar
authors.forename: Yong-Min
authors.initials: YM
authors.lastname: Lee
authors.forename: Jung Yoon
authors.initials: JY
authors.lastname: Lee
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
mesh_terms: D006859:Hydrogen / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D014867:Water / Q000737:chemistry*
chemical_list: D010087:Oxides; D011166:Porphyrins; D014867:Water; D008345:Manganese; D006859:Hydrogen