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论文类型：期刊论文

发表时间：2007-08-20

发表刊物：INORGANIC CHEMISTRY

收录刊物：SCIE

卷号：46

期号：17

页面范围：7075-7086

ISSN号：0020-1669

摘要：A detailed computational study of O-O bond formation, catalyzed by monomeric and dimeric Mn-corrole complexes, is reported. The model explicitly takes into account the solvent, with respect to the first and second coordination spheres, while the bulk solvent is described by the polarizable continuum model. Two reaction mechanisms are proposed and computationally characterized: the concerted and the two-step mechanisms. The concerted mechanism is based on a OH--(MnO)-O-IV interaction via the outer-sphere pathway involving the bridging solvent molecules in the first coordinating sphere. The two-step mechanism is proposed to operate via the coordination of a hydroxide to the Mn-Iv ion, forming a MnO(OH)(-)-corrole complex with a strongly nonplanar corrole ligand. Comparison of the proposed mechanisms with available experimental data. is performed.