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dc.contributor.authorZexing Cao
dc.contributor.author曹泽星
dc.contributor.authorXi Jin
dc.contributor.authorZhaohui Zhou
dc.contributor.author周朝晖
dc.contributor.authorQianer Zhang
dc.contributor.author张乾二
dc.date.accessioned2011-08-31T13:17:54Z
dc.date.available2011-08-31T13:17:54Z
dc.date.issued2006-03
dc.identifier.citationINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,2006,106(9):2161-2168zh_CN
dc.identifier.issn0020-7608
dc.identifier.urihttp://dx.doi.org/doi:10.1002/qua.20987
dc.identifier.urihttps://dspace.xmu.edu.cn/handle/2288/10704
dc.description.abstractProtonation of the metal-bound oxy-bidentate ligand in the model complexes of [(HS)(3)(NH3)M(OCH2COO)](q) (M = Mo, Fe, V, Co; q = -2, -1) in the gas phase and in solutions of water and acetonitrile has been explored by the density functional approach. Calculations show that protonation of the carboxyl oxygen can open the alpha-hydroxycarboxylate chelate ring ligated to a transition-metal center under specific oxidation and spin states. The feasibility of the chelate ring opening by protonation depends on the electronic nature of the metal site in tune with conversion of a six-coordinate with a five-coordinate metal atom. Such selective dissociation of the metal-bound chelate ligand manipulates the availability of an empty site at the metal center and significantly affects reactivity of the metal-mediated chemical processes. Protonation changes the stability of species with different spin multiplicities and impels spin transition at the metal center in dissociation of the oxy-bidentate ligand. Solvent environments of water and acetonitrile play an important role in stabilizing the negatively charged species. (C) 2006 Wiley Periodicals, Inc.zh_CN
dc.language.isoenzh_CN
dc.publisherJOHN WILEY & SONS INCzh_CN
dc.subjectdensity functional calculationszh_CN
dc.subjectprotonationzh_CN
dc.subjectchelate ring openingzh_CN
dc.subjecttransition metal-containing compoundszh_CN
dc.subjectnitrogenasezh_CN
dc.titleProtonation of metal-bound alpha-hydroxycarboxylate ligand and implication for the role of homocitrate in nitrogenase: Computational study of the oxy-bidentate chelate ring openingzh_CN
dc.typeArticlezh_CN


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