Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.date.accessioned | 2016-08-28T11:08:58Z | - |
dc.date.available | 2016-08-28T11:08:58Z | - |
dc.date.issued | 2002 | * |
dc.identifier.issn | 0947-6539 | * |
dc.identifier.other | OAK-1038 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/218985 | - |
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.language | English | * |
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.relation.issue | 9 | * |
dc.relation.volume | 8 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 2067 | * |
dc.relation.lastpage | 2071 | * |
dc.relation.journaltitle | Chemistry - A European Journal | * |
dc.identifier.doi | 10.1002/1521-3765(20020503)8:9< | * |
dc.identifier.doi | 2067::AID-CHEM2067> | * |
dc.identifier.doi | 3.0.CO | * |
dc.identifier.doi | 2-V | * |
dc.identifier.wosid | WOS:000175511000011 | * |
dc.identifier.scopusid | 2-s2.0-0037012717 | * |
dc.author.google | Nam W. | * |
dc.author.google | Kim I. | * |
dc.author.google | Lim M.H. | * |
dc.author.google | Choi H.J. | * |
dc.author.google | Lee J.S. | * |
dc.author.google | Jang H.G. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.date.modifydate | 20240116111857 | * |