Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Cho, Kyung-Bin | - |
dc.contributor.author | Kang, Hyeona | - |
dc.contributor.author | Woo, Jaeyoung | - |
dc.contributor.author | Park, Young Jun | - |
dc.contributor.author | Seo, Mi Sook | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Nam, Wonwoo | - |
dc.date.available | 2017-07-11T06:28:06Z | - |
dc.date.created | 2017-04-10 | - |
dc.date.issued | 2014-01-06 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/3130 | - |
dc.description.abstract | The mechanism of the C-H bond activation of hydrocarbons by a nonheme chromium(IV) oxo complex bearing an N-methylated tetraazamacrocyclic cyclam (TMC) ligand, [CrIV(O)(TMC)(Cl)]+ (2), has been investigated experimentally and theoretically. In experimental studies, reaction rates of 2 with substrates having weak C-H bonds were found to depend on the concentration and bond dissociation energies of the substrates. A large kinetic isotope effect value of 60 was determined in the oxidation of dihydroanthracene (DHA) and deuterated DHA by 2. These results led us to propose that the C-H bond activation reaction occurs via a H-atom abstraction mechanism, in which H-atom abstraction of substrates by 2 is the rate-determining step. In addition, formation of a chromium(III) hydroxo complex, [CrIII(OH)(TMC)(Cl)] + (3), was observed as a decomposed product of 2 in the C-H bond activation reaction. The CrIIIOH product was characterized unambiguously with various spectroscopic methods and X-ray crystallography. Density functional theory (DFT) calculations support the experimental observations that the C-H bond activation by 2 does not occur via the conventional H-atom-abstraction/oxygen-rebound mechanism and that 3 is the product formed in this C-H bond activation reaction. DFT calculations also propose that 2 may have some CrIIIO•- character. The oxidizing power of 2 was then compared with that of a chromium(III) superoxo complex bearing the identical TMC ligand, [CrIII(O 2)(TMC)(Cl)]+ (1), in the C-H bond activation reaction. By performing reactions of 1 and 2 with substrates under identical conditions, we were able to demonstrate that the reactivity of 2 is slightly greater than that of 1. DFT calculations again support this experimental observation, showing that the rate-limiting barrier for the reaction with 2 is slightly lower than that of 1. © 2013 American Chemical Society. | - |
dc.publisher | American Chemical Society | - |
dc.title | Mechanistic Insights into the C-H Bond Activation of Hydrocarbons by Chromium(IV) Oxo and Chromium(III) Superoxo Complexes | - |
dc.type | Article | - |
dc.identifier.doi | 10.1021/ic402831f | - |
dc.identifier.scopusid | 2-s2.0-84891814775 | - |
dc.identifier.bibliographicCitation | Inorganic Chemistry, v.53, no.1, pp.645 - 652 | - |
dc.subject.keywordPlus | HYDROGEN-ATOM ABSTRACTION | - |
dc.subject.keywordPlus | HIGH-VALENT IRON | - |
dc.subject.keywordPlus | DENSITY-FUNCTIONAL THEORY | - |
dc.subject.keywordPlus | ALPHA-HYDROXYLATING MONOOXYGENASE | - |
dc.subject.keywordPlus | SPIN OXOIRON(IV) COMPLEX | - |
dc.subject.keywordPlus | COPPER-DIOXYGEN ADDUCT | - |
dc.subject.keywordPlus | END-ON | - |
dc.subject.keywordPlus | HARTREE-FOCK | - |
dc.subject.keywordPlus | SPECTROSCOPIC CHARACTERIZATION | - |
dc.subject.keywordPlus | ALIPHATIC HYDROXYLATION | - |
dc.citation.endPage | 652 | - |
dc.citation.number | 1 | - |
dc.citation.startPage | 645 | - |
dc.citation.title | Inorganic Chemistry | - |
dc.citation.volume | 53 | - |
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