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| Type |
Poster Presentation |
| Area |
Inorganic Chemistry |
| Room No. |
Exhibition Hall 2+3 |
| Time |
10월 19일 (목요일) 11:00~12:30 |
| Code |
INOR.P-12 |
| Subject |
Unprecedented nitrile reactivity mediated by a peroxocobalt(III) intermediate |
| Authors |
Hyeonju Noh, Kyungmin Kim1, Jaeheung Cho*
Emerging Materials Science, Daegu Gyeongbuk Institute of Science & Technology, Korea
1School of Undergraduate Studies, Daegu Gyeongbuk Institute of Science & Technology, Korea
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| Abstract |
Oxidation processes mediated by metal-dioxygen adducts have attracted much attention in biomimetic and enzymatic reactions. Although a number of metal-dioxygen species have been prepared and investigated in oxidation reactions with diverse organic substrates under mild conditions, reactivities with nitriles have rarely been explored. Herein, we report that a side-on peroxocobalt(III) complex with a tetradentate macrocyclic ligand shows a novel and facile mode of dioxygenase-like reactivity with acetonitrile to give a mononuclear hydroximatocobalt(III) complex in which the nitrile is oxidized by two oxygen atoms of the peroxo group. 18O labeling experiments confirm that both oxygen atoms are derived from the peroxo ligand. This unprecedented mode of nitrile reactivity was also seen for other nitriles, e.g., CH3CH2CN and C6H5CN, each of which gives the corresponding hydroximatocobalt(III) complexes. Kinetic studies including the Hammett analysis and isotope labeling experiments suggest that this novel mode of nitrile activation occurs via a concerted mechanism. This new reaction will significantly expand the range of nitrile activation processes. |
| E-mail |
jooooo90@dgist.ac.kr |
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120th General Meeting of the KCS