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dc.contributor.author남원우*
dc.contributor.author이용민*
dc.date.accessioned2016-08-27T04:08:47Z-
dc.date.available2016-08-27T04:08:47Z-
dc.date.issued2015*
dc.identifier.issn0002-7863*
dc.identifier.otherOAK-15272*
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/217384-
dc.description.abstractA comprehensive experimental and theoretical study of the reactivity patterns and reaction mechanisms in alkane hydroxylation, olefin epoxidation, cyclohexene oxidation, and sulfoxidation reactions by a mononuclear nonheme ruthenium(IV)-oxo complex, [Ru-IV(O)(terpy)-(bpm)](2+) (1), has been conducted. In alkane hydroxylation (i.e., oxygen rebound vs oxygen non-rebound mechanisms), both the experimental and theoretical results show that the substrate radical formed via a rate-determining H atom abstraction of alkanes by 1 prefers dissociation over oxygen rebound and desaturation processes. In the oxidation of olefins by 1, the observations of a kinetic isotope effect (KIE) value of 1 and styrene oxide formation lead us to conclude that an epoxidation reaction via oxygen atom transfer (OAT) from the (RuO)-O-IV complex to the C=C double bond is the dominant pathway. Density functional theory (DFT) calculations show that the epoxidation reaction is a two-step, two-spin-state process. In contrast, the oxidation of cyclohexene by 1 affords products derived from allylic C-H bond oxidation, with a high KIE value of 38(3). The preference for H atom abstraction over C=C double bond epoxidation in the oxidation of cyclohexene by 1 is elucidated by DFT calculations, which show that the energy barrier for C-H activation is 4.5 kcal mol(-1) lower than the energy barrier for epoxidation. In the oxidation of sulfides, sulfoxidation by the electrophilic Ru-oxo group of 1 occurs via a direct OAT mechanism, and DFT calculations show that this is a two-spin-state reaction in which the transition state is the lowest in the S = 0 state.*
dc.languageEnglish*
dc.publisherAMER CHEMICAL SOC*
dc.titleInterplay of Experiment and Theory in Elucidating Mechanisms of Oxidation Reactions by a Nonheme (RuO)-O-IV Complex*
dc.typeArticle*
dc.relation.issue26*
dc.relation.volume137*
dc.relation.indexSCI*
dc.relation.indexSCIE*
dc.relation.indexSCOPUS*
dc.relation.startpage8623*
dc.relation.lastpage8632*
dc.relation.journaltitleJOURNAL OF THE AMERICAN CHEMICAL SOCIETY*
dc.identifier.doi10.1021/jacs.5b04787*
dc.identifier.wosidWOS:000357964400050*
dc.identifier.scopusid2-s2.0-84936792031*
dc.author.googleDhuri, Sunder N.*
dc.author.googleCho, Kyung-Bin*
dc.author.googleLee, Yong-Min*
dc.author.googleShin, Sun Young*
dc.author.googleKim, Jin Hwa*
dc.author.googleMandal, Debasish*
dc.author.googleShaik, Sason*
dc.author.googleNam, Wonwoo*
dc.contributor.scopusid남원우(7006569723)*
dc.contributor.scopusid이용민(36546331100;35233855500;57192113229)*
dc.date.modifydate20240130092654*
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자연과학대학 > 화학·나노과학전공 > Journal papers
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