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DC Field | Value | Language |
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dc.citation.endPage | 2071 | - |
dc.citation.number | 9 | - |
dc.citation.startPage | 2067 | - |
dc.citation.title | CHEMISTRY-A EUROPEAN JOURNAL | - |
dc.citation.volume | 8 | - |
dc.contributor.author | Nam, W | - |
dc.contributor.author | Kim, I | - |
dc.contributor.author | Lim, Mi Hee | - |
dc.contributor.author | Choi, HJ | - |
dc.contributor.author | Lee, JS | - |
dc.contributor.author | Jang, HG | - |
dc.date.accessioned | 2023-12-22T11:38:17Z | - |
dc.date.available | 2023-12-22T11:38:17Z | - |
dc.date.created | 2014-11-11 | - |
dc.date.issued | 2002-05 | - |
dc.description.abstract | The reaction of [Mn(TF4TMAP)](CF3SO3)5 (TF4TMAP = meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl)porphinato dianion) with H2O2 (2 equiv) at pH 10.5 and 0°C yielded an oxomanganese(V) porphyrin complex 1 in aqueous solution, whereas an oxomanganese(IV) porphyrin complex 2 was generated in the reactions of tert-alkyl hydroperoxides such as tert-butyl hydroperoxide and 2-methyl-l-phenyl-2-propyl hydroperoxide. Complex 1 was capable of epoxidizing olefins and exchanging its oxygen with H2 18O, whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF4TMAP)]5+ with various oxidants in the pH range 3-11, the O-O bond cleavage of hydroperoxides was found to be sensitive to the hydroperoxide substituent and the pH of the reaction solution. Whereas the O-O bond of hydroperoxides containing an electron-donating tert-alkyl group is cleaved homolytically, an electron-withdrawing substituent such as an acyl group in m-chloroperoxybenzoic acid (m-CPBA) facilitates O-O bond heterolysis. The mechanism of the O-O bond cleavage of H2O2 depends on the pH of the reaction solution: O-O bond homolysis prevails at low pH and O-O bond heterolysis becomes a predominant pathway at high pH. The effect of pH on 18O incorporation from H2 18O into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF4TMAP)]5+ and KHSO5 in buffered H2 18O solutions. A high proportion of 18O was incorporated into the CBZ-10,11-oxide product at all pH values but this proportion was not affected significantly by the pH of the reaction solution. | - |
dc.identifier.bibliographicCitation | CHEMISTRY-A EUROPEAN JOURNAL, v.8, no.9, pp.2067 - 2071 | - |
dc.identifier.doi | 10.1002/1521-3765(20020503)8:9<2067::AID-CHEM2067>3.0.CO;2-V | - |
dc.identifier.issn | 0947-6539 | - |
dc.identifier.scopusid | 2-s2.0-0037012717 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/8665 | - |
dc.identifier.url | http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=0037012717 | - |
dc.identifier.wosid | 000175511000011 | - |
dc.language | 영어 | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.title | Isolation of an oxomanganese(V) porphyrin intermediate in the reaction of a manganese(III) porphyrin complex and H2O2 in aqueous solution | - |
dc.type | Article | - |
dc.description.journalRegisteredClass | scopus | - |
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