DC Field | Value | Language |
---|---|---|
dc.contributor.author | Nam, W | ko |
dc.contributor.author | Kim, I | ko |
dc.contributor.author | Lim, Mi Hee | ko |
dc.contributor.author | Choi, HJ | ko |
dc.contributor.author | Lee, JS | ko |
dc.contributor.author | Jang, HG | ko |
dc.date.accessioned | 2018-02-21T06:25:48Z | - |
dc.date.available | 2018-02-21T06:25:48Z | - |
dc.date.created | 2018-02-08 | - |
dc.date.created | 2018-02-08 | - |
dc.date.created | 2018-02-08 | - |
dc.date.issued | 2002-05 | - |
dc.identifier.citation | CHEMISTRY-A EUROPEAN JOURNAL, v.8, no.9, pp.2067 - 2071 | - |
dc.identifier.issn | 0947-6539 | - |
dc.identifier.uri | http://hdl.handle.net/10203/240345 | - |
dc.description.abstract | The reaction of [Mn(TF(4)TMAP)](CF3SO3)(5) (TF(4)TMAP-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 degreesC yielded an oxomanganese(v) porphyrin complex I 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-1-phenyl-2-propyl hydroperoxide. Complex I was capable of' epoxidizing olefins and exchanging its oxygen with (H2O)-O-18. whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF(4)TMAP)](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 in-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 O-18 incorporation from (H2O)-O-18 into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF(4)TMAP)(5), and KHSO5 in buffered (H2O)-O-18 solutions. A high proportion of 110 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.language | English | - |
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.identifier.wosid | 000175511000011 | - |
dc.type.rims | ART | - |
dc.citation.volume | 8 | - |
dc.citation.issue | 9 | - |
dc.citation.beginningpage | 2067 | - |
dc.citation.endingpage | 2071 | - |
dc.citation.publicationname | CHEMISTRY-A EUROPEAN JOURNAL | - |
dc.identifier.doi | 10.1002/1521-3765(20020503)8:9<2067::AID-CHEM2067>3.0.CO;2-V | - |
dc.contributor.localauthor | Lim, Mi Hee | - |
dc.contributor.nonIdAuthor | Nam, W | - |
dc.contributor.nonIdAuthor | Kim, I | - |
dc.contributor.nonIdAuthor | Choi, HJ | - |
dc.contributor.nonIdAuthor | Lee, JS | - |
dc.contributor.nonIdAuthor | Jang, HG | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordAuthor | enzyme mimetics | - |
dc.subject.keywordAuthor | epoxidation | - |
dc.subject.keywordAuthor | heme proteins | - |
dc.subject.keywordAuthor | O-O activation | - |
dc.subject.keywordAuthor | porphyrinoids | - |
dc.subject.keywordPlus | WATER-SOLUBLE METALLOPORPHYRINS | - |
dc.subject.keywordPlus | HIGH-VALENT IRON | - |
dc.subject.keywordPlus | O BOND-CLEAVAGE | - |
dc.subject.keywordPlus | CYTOCHROME P450-CATALYZED HYDROXYLATION | - |
dc.subject.keywordPlus | TERT-BUTYL HYDROPEROXIDE | - |
dc.subject.keywordPlus | OXO-HYDROXO TAUTOMERISM | - |
dc.subject.keywordPlus | ALKYL HYDROPEROXIDES | - |
dc.subject.keywordPlus | CATALYZED EPOXIDATION | - |
dc.subject.keywordPlus | IRON(III) PORPHYRINS | - |
dc.subject.keywordPlus | MECHANISTIC PROBE | - |
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