DC Field | Value | Language |
---|---|---|
dc.contributor.author | Michel, C | - |
dc.contributor.author | Belanzoni, P | - |
dc.contributor.author | Gamez, P | - |
dc.contributor.author | Reedijk, J | - |
dc.contributor.author | Baerends, EJ | - |
dc.contributor.author | null | - |
dc.date.accessioned | 2016-04-01T08:18:49Z | - |
dc.date.available | 2016-04-01T08:18:49Z | - |
dc.date.issued | 2009-12 | - |
dc.identifier.citation | INORGANIC CHEMISTRY | - |
dc.identifier.citation | v.48 | - |
dc.identifier.citation | no.24 | - |
dc.identifier.citation | pp.11909-11920 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.other | 2009-OAK-0000019600 | - |
dc.identifier.uri | https://oasis.postech.ac.kr/handle/2014.oak/27694 | - |
dc.description.abstract | We have investigated the reaction mechanism of the selective aerobic oxidation of primary alcohols into aldehydes using a bipy-copper complex and the 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) radical as cocatalysts (Gamez et al. Chem. Commun. 2003, 2412-2415) and compared it to the well-known oxidation by the TEMPO+ ion. Our theoretical investigation shows that (a) the oxidation of alcohols to aldehydes by uncoordinated TEMPO+ takes place by electrophilic attack on the C-H-alpha bond of the alcohol | - |
dc.description.abstract | (b) the Cu(bipy)(2+) complex has two functions, namely, (1) it acts as a template that brings TEMPO and the (deprotonated) alcohol in proximity by coordinating these moieties in adjacent coordination sites, and (2) it oxidizes the TEMPO radical to (coordinated) TEMPO+ ion. The H abstraction from alcohol by TEMPO+ then proceeds as an intramolecular reaction, very much analogous to one of the reaction pathways with free TEMPO+ and with a remarkably low barrier. We stress that compared to other A-H bonds (A=C, N, O, F), the relatively high-lying C-H bonds are particularly susceptible to electrophilic attack, and notably the C-H-alpha bond next to the O in an alcohol is so because it is pushed up by an 0 lone pair Electrophilic attack, being common to the particular catalytic system studied in this paper and the well-known biotic and abiotic oxidation catalysis by heme and non-heme complexes of the ferryl ((FeO2+)-O-IV) ion, appears to be a unifying electronic structure principle of C-H-alpha hydroxylation and oxidation reactions. | - |
dc.description.statementofresponsibility | X | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | COPPER-CATALYZED OXIDATION | - |
dc.subject | GALACTOSE-OXIDASE | - |
dc.subject | SELECTIVE OXIDATION | - |
dc.subject | SCREENING MODEL | - |
dc.subject | SOLVATION | - |
dc.subject | EFFICIENT | - |
dc.subject | KETONES | - |
dc.subject | OXYGEN | - |
dc.subject | RADICALS | - |
dc.subject | LIQUID | - |
dc.title | "Activation of the C-H Bond by Electrophilic Attack: Theoretical Study of the Reaction Mechanism of the Aerobic Oxidation of Alcohols to Aldehydes by the Cu(bipy)(2+)/2,2,6,6-Tetramethylpiperidinyl-1-oxy Cocatalyst System" | - |
dc.type | Article | - |
dc.identifier.doi | 10.1021/IC902155M | - |
dc.author.google | Michel, C | - |
dc.author.google | Belanzoni, P | - |
dc.author.google | Gamez, P | - |
dc.author.google | Reedijk, J | - |
dc.author.google | Baerends, EJ | - |
dc.relation.volume | 48 | - |
dc.relation.issue | 24 | - |
dc.relation.startpage | 11909 | - |
dc.relation.lastpage | 11920 | - |
dc.publisher.location | US | - |
dc.relation.journal | INORGANIC CHEMISTRY | - |
dc.relation.index | SCI급, SCOPUS 등재논문 | - |
dc.collections.name | Journal Papers | - |
dc.type.docType | Article | - |
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