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dc.contributor.author남원우*
dc.contributor.author이용민*
dc.contributor.author박영준*
dc.date.accessioned2016-08-28T11:08:57Z-
dc.date.available2016-08-28T11:08:57Z-
dc.date.issued2016*
dc.identifier.issn0002-7863*
dc.identifier.otherOAK-18974*
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/218351-
dc.description.abstractMetal nitrosyl complexes are key intermediates involved in many biological and physiological processes of nitric oxide (NO) activation by metalloproteins. In this study, we report the reactivities of mononuclear cobalt(III)-nitrosyl complexes bearing N-tetramethylated cyclam (TMC) ligands, [(14-TMC)Co-III(NO)](2+) and [(12-TMC)Co-III(NO)](2+), in NO-transfer and dioxygenation reactions. The Co(III)-nitrosyl complex bearing 14-TMC ligand, [(14-TMC)Co-III(NO)](2+), transfers the bound nitrosyl ligand to [(12-TMC)Co-II(NO)](2+) via a dissociative pathway,-[[(14-TMC)Co-III(NO)](2+) (14-TMC)Co center dot center dot center dot NO}(2+)}, thus affording [(12-TMC)Co-III(NO)](2+) and [(14-TMC)Co-II](2+) as products. The dissociation of NO from the [(14-TMC)COIII(NO)](2+) complex prior to NO-transfer is supported experimentally and theoretically. In contrast, the reverse reaction, which is the NO-transfer from [(12-TMC)Co-III(NO)](2+) to [(14-TMC)Co-II](2+), does not occur. In addition to the NO-transfer reaction, dioxygenation of [(14-TMC)Co-III(NO)](2+) by O-2 produces [(14-TMC)Co-II(NO3)](+), which possesses an O,O-chelated nitrato ligand and where, based on an experiment using O-18-labeled O-2, two of the three O-atoms in the [(14-TMC)Co-II(NO3)](+) product derive from O-2. The dioxygenation reaction is proposed to occur via a dissociative pathway, as proposed in the NO-transfer reaction, and via the formation of a Co (II) peroxynitrite intermediate, based on the observation of phenol ring nitration. In contrast, [(12-TMC)Co-III(NO)](2+) does not react with O-2. Thus, the present results demonstrate unambiguously that the NO-transfer/dioxygenation reactivity of the cobalt(III)-nitrosyl complexes bearing TMC ligands is significantly influenced by the ring size of the TMC ligands and/or the spin state of the cobalt ion.*
dc.languageEnglish*
dc.publisherAMER CHEMICAL SOC*
dc.titleFactors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation*
dc.typeArticle*
dc.relation.issue24*
dc.relation.volume138*
dc.relation.indexSCIE*
dc.relation.indexSCOPUS*
dc.relation.startpage7753*
dc.relation.lastpage7762*
dc.relation.journaltitleJOURNAL OF THE AMERICAN CHEMICAL SOCIETY*
dc.identifier.doi10.1021/jacs.6b04040*
dc.identifier.wosidWOS:000378584600049*
dc.identifier.scopusid2-s2.0-84976388598*
dc.author.googleKumar, Pankaj*
dc.author.googleLee, Yong-Min*
dc.author.googleHu, Lianrui*
dc.author.googleChen, Jianwei*
dc.author.googlePark, Young Jun*
dc.author.googleYao, Jiannian*
dc.author.googleChen, Hui*
dc.author.googleKarlin, Kenneth D.*
dc.author.googleNam, Wonwoo*
dc.contributor.scopusid남원우(7006569723)*
dc.contributor.scopusid이용민(36546331100;35233855500;57192113229)*
dc.contributor.scopusid박영준(57205877314)*
dc.date.modifydate20240130092654*
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자연과학대학 > 화학·나노과학전공 > Journal papers
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