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dc.contributor.author남원우-
dc.date.accessioned2016-08-27T04:08:57Z-
dc.date.available2016-08-27T04:08:57Z-
dc.date.issued2016-
dc.identifier.issn0947-6539-
dc.identifier.issn1521-3765-
dc.identifier.otherOAK-16573-
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/218075-
dc.description.abstractWe report the Cu-I/O-2 chemistry of complexes derived from the macrocylic ligands 14-TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and 12-TMC (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). While [(14-TMC)Cu-I](+) is unreactive towards dioxygen, the smaller analog [(12-TMC)Cu-I(CH3CN)](+) reacts with O-2 to give a side-on bound peroxo-dicopper(II) species (P-S), confirmed by spectroscopic and computational methods. Intriguingly, 12-TMC as a N4 donor ligand generates (S)Pspecies, thus in contrast with the previous observation that such species are generated by N2 and N3 ligands. In addition, the reactivity of this macrocyclic side-on peroxo-dicopper(II) differs from typical (S)Pspecies, because it reacts only with acid to release H2O2, in contrast with the classic reactivity of Cu2O2 cores. Kinetics and computations are consistent with a protonation mechanism whereby the TMC acts as a hemilabile ligand and shuttles H+ to an isomerized peroxo core.-
dc.languageEnglish-
dc.publisherWILEY-V C H VERLAG GMBH-
dc.subjectbioinorganic chemistry-
dc.subjectcopper-
dc.subjectdioxygen reduction-
dc.subjectmacrocyclic ligands-
dc.subjectmetal-peroxo complexes-
dc.titleDioxygen Activation by a Macrocyclic Copper Complex Leads to a Cu2O2 Core with Unexpected Structure and Reactivity-
dc.typeArticle-
dc.relation.issue15-
dc.relation.volume22-
dc.relation.indexSCIE-
dc.relation.indexSCOPUS-
dc.relation.startpage5133-
dc.relation.lastpage5137-
dc.relation.journaltitleCHEMISTRY-A EUROPEAN JOURNAL-
dc.identifier.doi10.1002/chem.201600551-
dc.identifier.wosidWOS:000373483600012-
dc.identifier.scopusid2-s2.0-84959419442-
dc.author.googleGarcia-Bosch, Isaac-
dc.author.googleCowley, Ryan E.-
dc.author.googleDiaz, Daniel E.-
dc.author.googleSiegler, Maxime A.-
dc.author.googleNam, Wonwoo-
dc.author.googleSolomon, Edward I.-
dc.author.googleKarlin, Kenneth D.-
dc.contributor.scopusid남원우(7006569723)-
dc.date.modifydate20170601133726-
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자연과학대학 > 화학·나노과학전공 > Journal papers
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