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| Type |
Symposium |
| Area |
Recent Trends in Bio-Inorganic Chemistry |
| Room No. |
Room 211+212+213 |
| Time |
FRI 10:15-: |
| Code |
INOR1-4 |
| Subject |
Distinct Reactivity of a Mononuclear Peroxocobalt(III) Species towards Activation of Nitriles |
| Authors |
Jaeheung Cho
Emerging Materials Science, Daegu Gyeongbuk Institute of Science & Technology, Korea |
| Abstract |
The activation of nitriles is a field of synthetic interest for the preparation of materials important in fine chemical synthesis and pharmaceutical production, but typical methods have the disadvantage that strong bases or acids and high temperatures must be required. In this presentation, a mononuclear side-on peroxocobalt(III) complex with a tetradentate macrocyclic ligand, [Co(III)(TBDAP)(O2)]+ (1), shows a novel and facile mode of dioxygenase-like reactivity with nitriles (R-CN; R = Me, Et, and Ph) to produce the correspond-ing mononuclear hydroximatocobalt(III) complexes, [Co(III)(TBDAP)(R-C(=NO)O)]+, in which the nitrile moiety is oxidized by two oxygen atoms of the peroxo group. The overall reaction proceeds in one-pot under ambient conditions (ca. 1 hour, 40 °C). 18O-labeling experiments confirm that both oxygen atoms are derived from the peroxo ligand. The structures of all products, hydroximatocobalt(III) complexes, were confirmed by X-ray crystallography and various spectroscopic techniques. Kinetic studies including the Hammett analysis and isotope labeling experiments suggest that the mechanistic mode of 1 for activation of nitriles occurs via a concerted mechanism. This novel reaction would be significantly valuable for expanding the chemistry for nitrile activation and utilization. |
| E-mail |
jaeheung@dgist.ac.kr |
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120th General Meeting of the KCS