Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | - |
dc.contributor.author | Shunichi Fukuzumi | - |
dc.contributor.author | 이용민 | - |
dc.date.accessioned | 2024-08-26T16:31:11Z | - |
dc.date.available | 2024-08-26T16:31:11Z | - |
dc.date.issued | 2024 | - |
dc.identifier.issn | 2786-7863 | - |
dc.identifier.other | OAK-35755 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/269382 | - |
dc.description.abstract | The reaction of Li[(TAML)CoIII]·3H2O (TAML = tetraamido macrocyclic tetraanionic ligand) with iodosylbenzene at 253 K in acetone in the presence of redox-innocent metal ions (Sc(OTf)3 and Y(OTf)3) or triflic acid affords a blue species 1, which is converted reversibly to a green species 2 upon cooling to 193 K. The electronic structures of 1 and 2 have been determined by combining advanced spectroscopic techniques (X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), X-ray absorption spectroscopy/extended X-ray absorption fine structure (XAS/EXAFS), and magnetic circular dichroism (MCD)) with ab initio theoretical studies. Complex 1 is best represented as an S = 1/2 [(Sol)(TAML•+)CoIII-OH(LA)]− species (LA = Lewis/Brønsted acid and Sol = solvent), where an S = 1 Co(III) center is antiferromagnetically coupled to S = 1/2 TAML•+, which represents a one-electron oxidized TAML ligand. In contrast, complex 2, also with an S = 1/2 ground state, is found to be multiconfigurational with contributions of both the resonance forms [(H-TAML)CoIV═O(LA)]− and [(H-TAML•+)CoIII═O(LA)]−; H-TAML and H-TAML•+ represent the protonated forms of TAML and TAML•+ ligands, respectively. Thus, the interconversion of 1 and 2 is associated with a LA-associated tautomerization event, whereby H+ shifts from the terminal −OH group to TAML•+ with the concomitant formation of a terminal cobalt-oxo species possessing both singlet (SCo = 0) Co(III) and doublet (SCo = 1/2) Co(IV) characters. The reactivities of 1 and 2 at different temperatures have been investigated in oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactions to compare the activation enthalpies and entropies of 1 and 2. © 2024 American Chemical Society. | - |
dc.description.sponsorship | American Chemical Society | - |
dc.language | English | - |
dc.title | Identification, Characterization, and Electronic Structures of Interconvertible Cobalt-Oxygen TAML Intermediates | - |
dc.type | Article | - |
dc.relation.issue | 20 | - |
dc.relation.volume | 146 | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 13817 | - |
dc.relation.lastpage | 13835 | - |
dc.relation.journaltitle | Journal of the American Chemical Society | - |
dc.identifier.doi | 10.1021/jacs.3c14346 | - |
dc.identifier.wosid | WOS:001225206200001 | - |
dc.identifier.scopusid | 2-s2.0-85193028267 | - |
dc.author.google | Malik | - |
dc.author.google | Deesha D. | - |
dc.author.google | Ryu | - |
dc.author.google | Wooyeol | - |
dc.author.google | Kim | - |
dc.author.google | Yujeong | - |
dc.author.google | Singh | - |
dc.author.google | Gurjot | - |
dc.author.google | Jun-Hyeong | - |
dc.author.google | Sankaralingam | - |
dc.author.google | Muniyandi | - |
dc.author.google | Lee | - |
dc.author.google | Yong-Min | - |
dc.author.google | Seo | - |
dc.author.google | Mi Sook | - |
dc.author.google | Sundararajan | - |
dc.author.google | Mahesh | - |
dc.author.google | Ocampo | - |
dc.author.google | Daniel | - |
dc.author.google | Roemelt | - |
dc.author.google | Michael | - |
dc.author.google | Park | - |
dc.author.google | Kiyoung | - |
dc.author.google | Sun Hee | - |
dc.author.google | Baik | - |
dc.author.google | Mu-Hyun | - |
dc.author.google | Shearer | - |
dc.author.google | Jason | - |
dc.author.google | Ray | - |
dc.author.google | Kallol | - |
dc.author.google | Fukuzumi | - |
dc.author.google | Shunichi | - |
dc.author.google | Nam | - |
dc.author.google | Wonwoo | - |
dc.contributor.scopusid | 남원우(7006569723) | - |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | - |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | - |
dc.date.modifydate | 20240826133523 | - |