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题名: Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation
作者: Kumar, Pankaj1; Lee, Yong-Min1; Hu, Lianrui2; Chen, Jianwei2; Park, Young Jun1; Yao, Jiannian2; Chen, Hui2; Karlin, Kenneth D.3; Nam, Wonwoo1
刊名: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
发表日期: 2016-06-22
卷: 138, 期:24, 页:7753-7762
收录类别: SCI
英文摘要: Metal nitrosyl complexes are key intermediates involved in many biological and physiological processes of nitric oxide (NO) activation by metalloproteins. In this study, we report the reactivities of mononuclear cobalt(III)-nitrosyl complexes bearing N-tetramethylated cyclam (TMC) ligands, [(14-TMC)Co-III(NO)](2+) and [(12-TMC)Co-III(NO)](2+), in NO-transfer and dioxygenation reactions. The Co(III)-nitrosyl complex bearing 14-TMC ligand, [(14-TMC)Co-III(NO)](2+), transfers the bound nitrosyl ligand to [(12-TMC)Co-II(NO)](2+) via a dissociative pathway,-[[(14-TMC)Co-III(NO)](2+) (14-TMC)Co center dot center dot center dot NO}(2+)}, thus affording [(12-TMC)Co-III(NO)](2+) and [(14-TMC)Co-II](2+) as products. The dissociation of NO from the [(14-TMC)COIII(NO)](2+) complex prior to NO-transfer is supported experimentally and theoretically. In contrast, the reverse reaction, which is the NO-transfer from [(12-TMC)Co-III(NO)](2+) to [(14-TMC)Co-II](2+), does not occur. In addition to the NO-transfer reaction, dioxygenation of [(14-TMC)Co-III(NO)](2+) by O-2 produces [(14-TMC)Co-II(NO3)](+), which possesses an O,O-chelated nitrato ligand and where, based on an experiment using O-18-labeled O-2, two of the three O-atoms in the [(14-TMC)Co-II(NO3)](+) product derive from O-2. The dioxygenation reaction is proposed to occur via a dissociative pathway, as proposed in the NO-transfer reaction, and via the formation of a Co (II) peroxynitrite intermediate, based on the observation of phenol ring nitration. In contrast, [(12-TMC)Co-III(NO)](2+) does not react with O-2. Thus, the present results demonstrate unambiguously that the NO-transfer/dioxygenation reactivity of the cobalt(III)-nitrosyl complexes bearing TMC ligands is significantly influenced by the ring size of the TMC ligands and/or the spin state of the cobalt ion.
语种: 英语
内容类型: 期刊论文
URI标识: http://ir.iccas.ac.cn/handle/121111/35534
Appears in Collections:光化学实验室_期刊论文

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作者单位: 1.Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 120750, South Korea
2.Chinese Acad Sci, Beijing Natl Lab Mol Sci, Inst Chem, CAS Key Lab Photochem, Beijing 100190, Peoples R China
3.Johns Hopkins Univ, Dept Chem, Charles & 34Th St, Baltimore, MD 21218 USA
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