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dc.contributor.authorShunichi Fukuzumi-
dc.contributor.authorKenneth D. Karlin-
dc.date.accessioned2016-08-28T10:08:55Z-
dc.date.available2016-08-28T10:08:55Z-
dc.date.issued2013-
dc.identifier.issn0002-7863-
dc.identifier.otherOAK-10061-
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/223702-
dc.description.abstractA copper complex, [(PV-tmpa)CuII](ClO4)2 (1) [PV-tmpa = bis(pyrid-2-ylmethyl){[6-(pivalamido)pyrid-2-yl]methyl}amine], acts as a more efficient catalyst for the four-electron reduction of O 2 by decamethylferrocene (Fc*) in the presence of trifluoroacetic acid (CF3COOH) in acetone as compared with the corresponding copper complex without a pivalamido group, [(tmpa)Cu II](ClO4)2 (2) (tmpa = tris(2-pyridylmethyl) amine). The rate constant (kobs) of formation of decamethylferrocenium ion (Fc*+) in the catalytic four-electron reduction of O2 by Fc* in the presence of a large excess CF3COOH and O2 obeyed first-order kinetics. The k obs value was proportional to the concentration of catalyst 1 or 2, whereas the kobs value remained constant irrespective of the concentration of CF3COOH or O2. This indicates that electron transfer from Fc* to 1 or 2 is the rate-determining step in the catalytic cycle of the four-electron reduction of O2 by Fc* in the presence of CF3COOH. The second-order catalytic rate constant (kcat) for 1 is 4 times larger than the corresponding value determined for 2. With the pivalamido group in 1 compared to 2, the Cu II/CuI potentials are -0.23 and -0.05 V vs SCE, respectively. However, during catalytic turnover, the CF3COO - anion present readily binds to 2 shifting the resulting complex's redox potential to -0.35 V. The pivalamido group in 1 is found to inhibit anion binding. The overall effect is to make 1 easier to reduce (relative to 2) during catalysis, accounting for the relative kcat values observed. 1 is also an excellent catalyst for the two-electron two-proton reduction of H 2O2 to water and is also more efficient than is 2. For both complexes, reaction rates are greater than for the overall four-electron O2-reduction to water, an important asset in the design of catalysts for the latter. © 2013 American Chemical Society.-
dc.languageEnglish-
dc.titleEnhanced catalytic four-electron dioxygen (O2) and two-electron hydrogen peroxide (H2O2) reduction with a copper(II) complex possessing a pendant ligand pivalamido group-
dc.typeArticle-
dc.relation.issue17-
dc.relation.volume135-
dc.relation.indexSCI-
dc.relation.indexSCIE-
dc.relation.indexSCOPUS-
dc.relation.startpage6513-
dc.relation.lastpage6522-
dc.relation.journaltitleJournal of the American Chemical Society-
dc.identifier.doi10.1021/ja3125977-
dc.identifier.wosidWOS:000318469100026-
dc.identifier.scopusid2-s2.0-84877054910-
dc.author.googleKakuda S.-
dc.author.googlePeterson R.L.-
dc.author.googleOhkubo K.-
dc.author.googleKarlin K.D.-
dc.author.googleFukuzumi S.-
dc.contributor.scopusidShunichi Fukuzumi(35430038100;57375583300)-
dc.date.modifydate20220119145616-
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자연과학대학 > 화학·나노과학전공 > Journal papers
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