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dc.contributor.authorZhu, Chunzh_CN
dc.contributor.authorLiang, Jinxiazh_CN
dc.contributor.authorWang, Binjuzh_CN
dc.contributor.authorZhu, Junzh_CN
dc.contributor.authorCao, Zexingzh_CN
dc.contributor.author曹泽星zh_CN
dc.contributor.author朱军zh_CN
dc.date.accessioned2013-12-12T02:12:24Z
dc.date.available2013-12-12T02:12:24Z
dc.date.issued2012zh_CN
dc.identifier.citationPhysical Chemistry Chemical Physics,14(37):12800-12806zh_CN
dc.identifier.issn1463-9076zh_CN
dc.identifier.otherWOS:000308101100013zh_CN
dc.identifier.urihttps://dspace.xmu.edu.cn/handle/2288/62108
dc.descriptionMinistry of Science and Technology [2011CB808504, 2012CB214900]; National Science Foundation of China [21133007, 21172184]zh_CN
dc.description.abstractThe electronic and structural features of (oxo)manganese(V) corroles and their catalyzed oxygen atom transfers to thioanisole in different spin states have been investigated by the B3LYP functional calculations. Calculations show that these corrole-based oxidants and their complexes with thioanisole generally have the singlet ground state, and their triplet forms are also accessible in consideration of the spin-orbit coupling interaction. Due to strong d-pi conjugation interactions between Mn and the corrole ring arising from the p electron donation of the corrole moiety, the five-coordinated Mn approximately has the stable 18-electron configuration. The predicted free energy barriers for the singlet oxygen atom transfer reactions are generally larger than 22 kcal mol(-1), while the spin flip in reaction may remarkably increase the reactivity. In particular, the bromination on beta-pyrrole carbon atoms of the meso-substituted (oxo)manganese(V) corrole strikingly enhances the spin-orbit coupling interaction and results in the dramatic increase of reactivity. The multiple spin changes are predicted to be involved in the low-energy reaction pathway. The present results show good agreement with the experimental observation and provide a detailed picture for the oxygen atom transfer reaction induced by the (oxo) manganese(V) corroles.zh_CN
dc.language.isoen_USzh_CN
dc.source.urihttp://dx.doi.org/10.1039/c2cp41647fzh_CN
dc.subjectFLASH-PHOTOLYSIS GENERATIONzh_CN
dc.subjectCYTOCHROME-P450 ENZYMESzh_CN
dc.subjectCORRELATION-ENERGYzh_CN
dc.subjectMANGANESE CORROLEzh_CN
dc.subjectIRON COMPLEXESzh_CN
dc.subjectMILD OXIDATIONzh_CN
dc.subjectSTATESzh_CN
dc.subjectEPOXIDATIONzh_CN
dc.subjectMECHANISMzh_CN
dc.subjectCATALYSISzh_CN
dc.titleSignificant effect of spin flip on the oxygen atom transfer reaction from (oxo)manganese(v) corroles to thioanisole: insights from density functional calculationszh_CN
dc.typeArticlezh_CN


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