Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 이용민 | * |
dc.contributor.author | Kenneth D. Karlin | * |
dc.date.accessioned | 2016-08-28T10:08:29Z | - |
dc.date.available | 2016-08-28T10:08:29Z | - |
dc.date.issued | 2013 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-9788 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223458 | - |
dc.description.abstract | Selective two-electron plus two-proton (2e-/2H+) reduction of O2 to hydrogen peroxide by ferrocene (Fc) or 1,1′-dimethylferrocene (Me2Fc) in the presence of perchloric acid is catalyzed efficiently by a mononuclear copper(II) complex, [Cu II(tepa)]2+ (1; tepa = tris[2-(2-pyridyl)ethyl]amine) in acetone. The E1/2 value for [CuII(tepa)]2+ as measured by cyclic voltammetry is 0.07 V vs Fc/Fc+ in acetone, being significantly positive, which makes it possible to use relatively weak one-electron reductants such as Fc and Me2Fc for the overall two-electron reduction of O2. Fast electron transfer from Fc or Me2Fc to 1 affords the corresponding CuI complex [Cu I(tepa)]+ (2), which reacts at low temperature (193 K) with O2, however only in the presence of HClO4, to afford the hydroperoxo complex [CuII(tepa)(OOH)]+ (3). A detailed kinetic study on the homogeneous catalytic system reveals the rate-determining step to be the O2-binding process in the presence of HClO4 at lower temperature as well as at room temperature. The O2-binding kinetics in the presence of HClO4 were studied, demonstrating that the rate of formation of the hydroperoxo complex 3 as well as the overall catalytic reaction remained virtually the same with changing temperature. The apparent lack of activation energy for the catalytic two-electron reduction of O2 is shown to result from the existence of a pre-equilibrium between 2 and O2 prior to the formation of the hydroperoxo complex 3. No further reduction of [CuII(tepa)(OOH)]+ (3) by Fc or Me2Fc occurred, and instead 3 is protonated by HClO4 to yield H2O2 accompanied by regeneration of 1, thus completing the catalytic cycle for the two-electron reduction of O2 by Fc or Me2Fc. © 2013 American Chemical Society. | * |
dc.language | English | * |
dc.title | Temperature-independent catalytic two-electron reduction of dioxygen by ferrocenes with a copper(II) tris[2-(2-pyridyl)ethyl]amine catalyst in the presence of perchloric acid | * |
dc.type | Article | * |
dc.relation.issue | 7 | * |
dc.relation.volume | 135 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 2825 | * |
dc.relation.lastpage | 2834 | * |
dc.relation.journaltitle | Journal of the American Chemical Society | * |
dc.identifier.doi | 10.1021/ja312523u | * |
dc.identifier.wosid | WOS:000315373000063 | * |
dc.identifier.scopusid | 2-s2.0-84874032643 | * |
dc.author.google | Das D. | * |
dc.author.google | Lee Y.-M. | * |
dc.author.google | Ohkubo K. | * |
dc.author.google | Nam W. | * |
dc.author.google | Karlin K.D. | * |
dc.author.google | Fukuzumi S. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240802081000 | * |