Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Lee, Yuri | - |
dc.contributor.author | Kim, Bohee | - |
dc.contributor.author | Kim, Seonghan | - |
dc.contributor.author | Ng, Elvis Wang Hei | - |
dc.contributor.author | Ariyasu, Shinya | - |
dc.contributor.author | Shoji, Osami | - |
dc.contributor.author | Yoon, Sungho | - |
dc.contributor.author | Hirao, Hajime | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.date.accessioned | 2024-04-15T09:10:15Z | - |
dc.date.available | 2024-04-15T09:10:15Z | - |
dc.date.created | 2024-03-07 | - |
dc.date.issued | 2024-02 | - |
dc.identifier.issn | 2155-5435 | - |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/56559 | - |
dc.description.abstract | Oxidation of unactivated alkanes, which requires substantial energy for conversion to valuable organic chemicals, is a major challenge in both industry and academia. Herein, we describe how solvents affect and improve the catalytic oxidation ability of a mononuclear copper(II)-alkylperoxo complex, [CuII(iPr3-tren)(OOC(CH3)2Ph)]+ (1, iPr3-tren = tris[2-(isopropylamino)ethyl]amine), toward hydrocarbon substrates. 1 was prepared by adding cumene hydroperoxide and triethylamine to the solution of [Cu(iPr3-tren)(CH3CN)]2+, which was characterized using various physicochemical methods. Product analyses, along with theoretical calculations, indicate that homolytic O-O bond cleavage occurs during the thermal decomposition of 1 at 60 °C in various solvents such as CH3CN, CH3COCH3, C6H5CF3, and C6H6. Both experimental results and density functional theory (DFT) calculations supported variations in the catalytic activity of 1 depending on solvents. In CH3CN and CH3COCH3, 1 activates weak C-H bonds (bond dissociation energy (BDE) ≤ ∼81.6 kcal mol-1), while 1 in C6H5CF3 and C6H6 can oxidize slightly stronger C-H bonds with a BDE of up to 84.5 kcal mol-1. In supercritical carbon dioxide (SC-CO2), 1 can oxidize alkanes with strong C-H bonds, such as cyclohexane (99.5 kcal mol-1). The enhanced C-H bond oxidation of 1 in C6H5CF3, C6H6, and SC-CO2 was generally attributed to two different factors: (a) the nonpolarity of the solvent and (b) the absence of C(sp3)-H bonds in the solvent. Interestingly, in CH2Cl2, a nonpolar solvent with C(sp3)-H bonds, 1 exhibited similar reactivity to that in C6H5CF3, indicating that nonpolar solvents enhance the catalytic ability of copper(II)-cumylperoxo complex to abstract hydrogen atoms from substrates, regardless of the presence of C(sp3)-H bonds in solvent molecules. DFT calculations employing an implicit solvent model further supported the enhanced reactivity, without the need to account for the presence of a C(sp3)-H bond. The reactivity of the different possible reactive intermediates arising from the catalytic oxidation was also explored using DFT calculations. This study provides a perspective on how solvents can be utilized to modulate the catalytic effects on C-H bond activation. © 2024 American Chemical Society | - |
dc.language | English | - |
dc.publisher | American Chemical Society | - |
dc.title | Influence of Solvents on Catalytic C-H Bond Oxidation by a Copper(II)-Alkylperoxo Complex | - |
dc.type | Article | - |
dc.identifier.doi | 10.1021/acscatal.3c05643 | - |
dc.identifier.wosid | 001173670600001 | - |
dc.identifier.scopusid | 2-s2.0-85186073183 | - |
dc.identifier.bibliographicCitation | ACS Catalysis, v.14, no.5, pp.3524 - 3532 | - |
dc.description.isOpenAccess | FALSE | - |
dc.subject.keywordAuthor | copper(II)-alkylperoxo complex | - |
dc.subject.keywordAuthor | catalytic reactions | - |
dc.subject.keywordAuthor | C-H bond activation | - |
dc.subject.keywordAuthor | solvent effects | - |
dc.subject.keywordAuthor | reaction mechanisms | - |
dc.subject.keywordPlus | ELECTRONIC-STRUCTURE | - |
dc.subject.keywordPlus | REACTIVITY | - |
dc.subject.keywordPlus | COPPER | - |
dc.subject.keywordPlus | HYDROXYLATION | - |
dc.subject.keywordPlus | MECHANISM | - |
dc.subject.keywordPlus | CLEAVAGE | - |
dc.subject.keywordPlus | SCISSION | - |
dc.subject.keywordPlus | RADICALS | - |
dc.subject.keywordPlus | MODELS | - |
dc.subject.keywordPlus | LIGAND | - |
dc.citation.endPage | 3532 | - |
dc.citation.number | 5 | - |
dc.citation.startPage | 3524 | - |
dc.citation.title | ACS Catalysis | - |
dc.citation.volume | 14 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Physical | - |
dc.type.docType | Article | - |
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