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dc.contributor.author남원우*
dc.date.accessioned2016-08-28T11:08:58Z-
dc.date.available2016-08-28T11:08:58Z-
dc.date.issued2002*
dc.identifier.issn0947-6539*
dc.identifier.otherOAK-1038*
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/218985-
dc.description.abstractThe 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.languageEnglish*
dc.titleIsolation of an oxomanganese(v) porphyrin intermediate in the reaction of a manganese(III) porphyrin complex and H2O2 in aqueous solution*
dc.typeArticle*
dc.relation.issue9*
dc.relation.volume8*
dc.relation.indexSCI*
dc.relation.indexSCIE*
dc.relation.indexSCOPUS*
dc.relation.startpage2067*
dc.relation.lastpage2071*
dc.relation.journaltitleChemistry - A European Journal*
dc.identifier.doi10.1002/1521-3765(20020503)8:9&lt*
dc.identifier.doi2067::AID-CHEM2067&gt*
dc.identifier.doi3.0.CO*
dc.identifier.doi2-V*
dc.identifier.wosidWOS:000175511000011*
dc.identifier.scopusid2-s2.0-0037012717*
dc.author.googleNam W.*
dc.author.googleKim I.*
dc.author.googleLim M.H.*
dc.author.googleChoi H.J.*
dc.author.googleLee J.S.*
dc.author.googleJang H.G.*
dc.contributor.scopusid남원우(7006569723)*
dc.date.modifydate20240116111857*
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자연과학대학 > 화학·나노과학전공 > Journal papers
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