Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 남원우 | * |
dc.contributor.author | 조재흥 | * |
dc.date.accessioned | 2016-08-28T12:08:57Z | - |
dc.date.available | 2016-08-28T12:08:57Z | - |
dc.date.issued | 2010 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-7103 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/221212 | - |
dc.description.abstract | Metal-dioxygen adducts are key intermediates detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. In this study, mononuclear cobalt(III)-peroxo complexes bearing tetraazamacrocyclic ligands, [Co(12-TMC)(O 2)] + and [Co(13-TMC)(O 2)] +, were synthesized by reacting [Co(12-TMC)(CH 3CN)] 2+ and [Co(13-TMC)(CH 3CN)] 2+, respectively, with H 2O 2 in the presence of triethylamine. The mononuclear cobalt(III)-peroxo intermediates were isolated and characterized by various spectroscopic techniques and X-ray crystallography, and the structural and spectroscopic characterization demonstrated unambiguously that the peroxo ligand is bound in a side-on η 2 fashion. The O-O bond stretching frequency of [Co(12-TMC)(O 2)] + and [Co(13-TMC)(O 2)] + was determined to be 902 cm -1 by resonance Raman spectroscopy. The structural properties of the CoO 2 core in both complexes are nearly identical; the O-O bond distances of [Co(12-TMC)(O 2)] + and [Co(13-TMC)(O 2)] + were 1.4389(17) Å and 1.438(6) Å, respectively. The cobalt(III)-peroxo complexes showed reactivities in the oxidation of aldehydes and O 2-transfer reactions. In the aldehyde oxidation reactions, the nucleophilic reactivity of the cobalt-peroxo complexes was significantly dependent on the ring size of the macrocyclic ligands, with the reactivity of [Co(13-TMC)(O 2)] + > [Co(12-TMC)(O 2)] +. In the O 2-transfer reactions, the cobalt(III)-peroxo complexes transferred the bound peroxo group to a manganese(II) complex, affording the corresponding cobalt(II) and manganese(III)-peroxo complexes. The reactivity of the cobalt-peroxo complexes in O 2-transfer was also significantly dependent on the ring size of tetraazamacrocycles, and the reactivity order in the O 2-transfer reactions was the same as that observed in the aldehyde oxidation reactions. © 2010 American Chemical Society. | * |
dc.language | English | * |
dc.title | Synthesis, structural, and spectroscopic characterization and reactivities of mononuclear cobalt(III)-peroxo complexes | * |
dc.type | Article | * |
dc.relation.issue | 47 | * |
dc.relation.volume | 132 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 16977 | * |
dc.relation.lastpage | 16986 | * |
dc.relation.journaltitle | Journal of the American Chemical Society | * |
dc.identifier.doi | 10.1021/ja107177m | * |
dc.identifier.wosid | WOS:000284972400041 | * |
dc.identifier.scopusid | 2-s2.0-78649526666 | * |
dc.author.google | Cho J. | * |
dc.author.google | Sarangi R. | * |
dc.author.google | Kang H.Y. | * |
dc.author.google | Lee J.Y. | * |
dc.author.google | Kubo M. | * |
dc.author.google | Ogura T. | * |
dc.author.google | Solomon E.I. | * |
dc.author.google | Nam W. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | 조재흥(7403536408) | * |
dc.date.modifydate | 20240116111857 | * |