Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | 이용민 | * |
dc.date.accessioned | 2016-08-27T04:08:47Z | - |
dc.date.available | 2016-08-27T04:08:47Z | - |
dc.date.issued | 2015 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-15272 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/217384 | - |
dc.description.abstract | A 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.language | English | * |
dc.publisher | AMER CHEMICAL SOC | * |
dc.title | Interplay of Experiment and Theory in Elucidating Mechanisms of Oxidation Reactions by a Nonheme (RuO)-O-IV Complex | * |
dc.type | Article | * |
dc.relation.issue | 26 | * |
dc.relation.volume | 137 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 8623 | * |
dc.relation.lastpage | 8632 | * |
dc.relation.journaltitle | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | * |
dc.identifier.doi | 10.1021/jacs.5b04787 | * |
dc.identifier.wosid | WOS:000357964400050 | * |
dc.identifier.scopusid | 2-s2.0-84936792031 | * |
dc.author.google | Dhuri, Sunder N. | * |
dc.author.google | Cho, Kyung-Bin | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Shin, Sun Young | * |
dc.author.google | Kim, Jin Hwa | * |
dc.author.google | Mandal, Debasish | * |
dc.author.google | Shaik, Sason | * |
dc.author.google | Nam, Wonwoo | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240130092654 | * |