Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | 이용민 | * |
dc.contributor.author | 서미숙 | * |
dc.contributor.author | 김진 | * |
dc.date.accessioned | 2023-01-06T16:31:05Z | - |
dc.date.available | 2023-01-06T16:31:05Z | - |
dc.date.issued | 2022 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.issn | 1520-5126 | * |
dc.identifier.other | OAK-32758 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/263104 | - |
dc.description.abstract | High-valent first-row transition-metal-oxo complexes are impor-tant intermediates in biologically and chemically relevant oxidative transformations of organic molecules and in the water splitting reaction in (artificial) photosynthesis. While high-valent Fe- and Mn-oxo complexes have been characterized in detail, much less is known about their analogues with late transition metals. In this study, we present the synthesis and detailed characterization of a unique mononuclear terminal Ni-O complex. This compound, [Ni(TAML)(O)(OH)]3-, is characterized by an intense charge -transfer (CT) band around 730 nm and has an St = 1 ground state, as determined by magnetic circular dichroism spectroscopy. From extended X-ray absorption fine structure (EXAFS), the Ni-O bond distance is 1.84 angstrom. Ni K edge XAS data indicate that the complex contains a Ni(III) center, which results from an unusually large degree of Ni-O pi-bond inversion, with one hole located on the oxo ligand. The complex is therefore best described as a low-spin Ni(III) complex (S = 1/2) with a bound oxyl (O center dot-) ligand (S = 1/2), where the spins of Ni and oxyl are ferromagnetically coupled, giving rise to the observed St = 1 ground state. This bonding description is roughly equivalent to the presence of a Ni-O single (sigma) bond. Reactivity studies show that [Ni(TAML)(O)(OH)]3- is a strong oxidant capable of oxidizing thioanisole and styrene derivatives with large negative rho values in the Hammett plot, indicating its electrophilic nature. The intermediate also shows high reactivity in C-H bond activation of hydrocarbons with a kinetic isotope effect of 7.0(3) in xanthene oxidation. | * |
dc.language | English | * |
dc.publisher | AMER CHEMICAL SOC | * |
dc.title | Preparation and Characterization of a Formally NiIV-Oxo Complex with a Triplet Ground State and Application in Oxidation Reactions br | * |
dc.type | Article | * |
dc.relation.issue | 49 | * |
dc.relation.volume | 144 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 22698 | * |
dc.relation.lastpage | 22712 | * |
dc.relation.journaltitle | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | * |
dc.identifier.doi | 10.1021/jacs.2c10196 | * |
dc.identifier.wosid | WOS:000892621700001 | * |
dc.identifier.scopusid | 2-s2.0-85143434617 | * |
dc.author.google | Karmalkar, Deepika G. | * |
dc.author.google | Larson, Virginia A. | * |
dc.author.google | Malik, Deesha D. | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Seo, Mi Sook | * |
dc.author.google | Kim, Jin | * |
dc.author.google | Vasiliauskas, Dovydas | * |
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.contributor.scopusid | 김진(55966696700) | * |
dc.date.modifydate | 20240426135715 | * |