title: Catalytic Radical Reduction in Aqueous Solution by a Ruthenium Hydride Intermediate.
abstract: Some manganese complexes can catalyze both antioxidant and pro-oxidant reactions, whereby the disparate reactivity modes are determined by the catalyst environment and afford distinct therapeutic effects. We recently reported the reduction of radicals in buffered aqueous solution catalyzed by a ruthenium complex with biologically relevant non-tertiary alcohols as terminal reductants. Mechanistic evidence is presented, indicating that this catalytic radical reduction is achieved by a Ru-hydride intermediate formed by β-hydride elimination from a Ru-alkoxide species. A similar mechanism and Ru-hydride intermediate was previously reported to kill cancer cells with catalytic pro-oxidant effects. Therefore, our demonstration of catalytic antioxidant effects by the same type of intermediate reveals new potential therapeutic strategies and applications for catalytic systems that form Ru-hydride intermediates.
authors.affiliation: Department of Chemistry, Clemson University, Clemson, SC, 29634, USA.
authors.forename: Yamin
authors.identifier: 0000-0002-8402-1372
authors.initials: Y
authors.lastname: Htet
authors.affiliation: Department of Chemistry, Clemson University, Clemson, SC, 29634, USA. atennys@clemson.edu.|Department of Materials Science and Engineering, Clemson University, Clemson, SC, 29634, USA. atennys@clemson.edu.|Center for Optical Materials Science and Engineering Technologies, 91 Technology Drive, Anderson, SC, 29625, USA. atennys@clemson.edu.
authors.forename: Andrew G
authors.identifier: 0000-0002-8593-2979
authors.initials: AG
authors.lastname: Tennyson
keywords: carbene ligands; dehydrogenation; electron transfer; radical reactions; ruthenium