Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | 이용민 | * |
dc.contributor.author | 서미숙 | * |
dc.date.accessioned | 2021-12-01T16:31:02Z | - |
dc.date.available | 2021-12-01T16:31:02Z | - |
dc.date.issued | 2021 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.issn | 1520-5126 | * |
dc.identifier.other | OAK-30522 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/259636 | - |
dc.description.abstract | In this paper, we report the preparation, spectro-scopic and theoretical characterization, and reactivity studies of a Co(IV)-oxo complex bearing an N4-macrocyclic coligand, 12-TBC (12-TBC = 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclododecane). On the basis of the ligand and the structure of the Co(II) precursor, [Co-II(12-TBC)(CF3SO3)(2)], one would assume that this species corresponds to a tetragonal Co(IV)-oxo complex, but the spectroscopic data do not support this notion. Co K-edge XAS data show that the treatment of the Co( II) precursor with iodosylbenzene (PhIO) as an oxidant at -40 degrees C in the presence of a proton source leads to a distinct shift in the Co K-edge, in agreement with the formation of a Co(IV) intermediate. The presence of the oxo group is further demonstrated by resonance Raman (rRaman) spectroscopy. Interestingly, the EPR data of this complex show a high degree of rhombicity, indicating structural distortion. This is further supported by the EXAFS data. Using DFT calculations, a structural model is developed for this complex with a ligand-protonated structure that features a Co = O center dot center dot center dot HN hydrogen bond and a four-coordinate Co center in a seesaw-shaped coordination geometry. Magnetic circular dichroism (MCD) spectroscopy further supports this finding. The hydrogen bond leads to an interesting polarization of the Co-oxo pi-bonds, where one O(p) lone-pair is stabilized and leads to a regular Co(d) interaction, whereas the other pi-bond shows an inverted ligand field. The reactivity of this complex in hydrogen atom and oxygen atom transfer reactions is discussed as well. | * |
dc.language | English | * |
dc.publisher | AMER CHEMICAL SOC | * |
dc.title | The Oxo-Wall Remains Intact: A Tetrahedrally Distorted Co(IV)-Oxo Complex | * |
dc.type | Article | * |
dc.relation.issue | 41 | * |
dc.relation.volume | 143 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 16943 | * |
dc.relation.lastpage | 16959 | * |
dc.relation.journaltitle | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | * |
dc.identifier.doi | 10.1021/jacs.1c04919 | * |
dc.identifier.wosid | WOS:000710935500010 | * |
dc.author.google | Yang, Jindou | * |
dc.author.google | Dong, Hai T. | * |
dc.author.google | Seo, Mi Sook | * |
dc.author.google | Larson, Virginia A. | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Shearer, Jason | * |
dc.author.google | Lehnert, Nicolai | * |
dc.author.google | Nam, Wonwoo | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.contributor.scopusid | 서미숙(7101805112) | * |
dc.date.modifydate | 20240426135715 | * |