Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | Kenneth D. Karlin | * |
dc.date.accessioned | 2016-08-28T10:08:55Z | - |
dc.date.available | 2016-08-28T10:08:55Z | - |
dc.date.issued | 2013 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-10061 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223702 | - |
dc.description.abstract | A 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.language | English | * |
dc.title | Enhanced catalytic four-electron dioxygen (O2) and two-electron hydrogen peroxide (H2O2) reduction with a copper(II) complex possessing a pendant ligand pivalamido group | * |
dc.type | Article | * |
dc.relation.issue | 17 | * |
dc.relation.volume | 135 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 6513 | * |
dc.relation.lastpage | 6522 | * |
dc.relation.journaltitle | Journal of the American Chemical Society | * |
dc.identifier.doi | 10.1021/ja3125977 | * |
dc.identifier.wosid | WOS:000318469100026 | * |
dc.identifier.scopusid | 2-s2.0-84877054910 | * |
dc.author.google | Kakuda S. | * |
dc.author.google | Peterson R.L. | * |
dc.author.google | Ohkubo K. | * |
dc.author.google | Karlin K.D. | * |
dc.author.google | Fukuzumi S. | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.date.modifydate | 20240401081001 | * |