Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation
文献类型：期刊论文
| 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
 |
| 出版日期 | 2016-06-22 |
| 卷号 | 138期号:24页码:7753-7762 |
| 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. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/35534]  |
| 专题 | 化学研究所_光化学实验室 |
| 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 |
| 推荐引用方式 GB/T 7714 | Kumar, Pankaj,Lee, Yong-Min,Hu, Lianrui,et al. Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2016,138(24):7753-7762. |
| APA | Kumar, Pankaj.,Lee, Yong-Min.,Hu, Lianrui.,Chen, Jianwei.,Park, Young Jun.,...&Nam, Wonwoo.(2016).Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,138(24),7753-7762. |
| MLA | Kumar, Pankaj,et al."Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 138.24(2016):7753-7762. |
入库方式： OAI收割
来源：化学研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。