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Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation

Title
Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation
Authors
Kumar, PankajLee, Yong-MinHu, LianruiChen, JianweiPark, Young JunYao, JiannianChen, HuiKarlin, Kenneth D.Nam, Wonwoo
Ewha Authors
남원우이용민박영준
SCOPUS Author ID
남원우scopus; 이용민scopusscopus
Issue Date
2016
Journal Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN
0002-7863JCR Link
Citation
vol. 138, no. 24, pp. 7753 - 7762
Publisher
AMER CHEMICAL SOC
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
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.
DOI
10.1021/jacs.6b04040
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자연과학대학 > 화학·나노과학전공 > Journal papers
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