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대한화학회 제124회 학술발표회 및 총회 First observation of nucleophilic reactivity for a copper(II)-hydroperoxo complex

등록일
2019년 7월 26일 13시 52분 38초
접수번호
0027
발표코드
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발표시간
목 09시 : 10분
발표형식
구두발표
발표분야
Inorganic Chemistry - Oral Presentation of Young Inorganic Chemistry
저자 및
공동저자
Bohee Kim, Jaeheung Cho1,*
Emerging Materials Science, Daegu Gyeongbuk Institute of Science & Technology, Korea
1Emerging Materials Science, DGIST, Korea

Copper(II)-hydroperoxo species are often detected as key intermediates in metalloenzymes and biomimetic compounds containing copper. However, the only reactivity has previously been observed for the copper(II)-hydroperoxo complexes is electrophilic, occurring through the O-O bond cleavage. Herein, we report that a mononuclear end-on copper(II)-hydroperoxo complex, which has been successfully characterized by various physicochemical methods including UV-vis, rRaman, CSI-MS and EPR, is a very reactive oxidant that utilizes a nucleophilic mechanism. In addition, DFT calculations fully support the electronic structure of this complex as a copper(II)-hydroperoxo complex with trigonal bipyramidal coordination geometry. A positive Hammett ρ value (2.0(3)) is observed in the reaction of copper(II)-hydroperoxo complex with para-substituted acyl chlorides, which clearly indicates nucleophilic character for the copper(II)-hydroperoxo complex. The copper(II)-hydroperoxo complex is an especially reactive oxidant in aldehyde deformylation with 2-PPA and CCA relative to the other metal-bound reactive oxygen species reported so far. The observation of nucleophilic reactivity for a copper(II)-hydroperoxo species significantly expands the known chemistry of metal-reactive oxygen species.

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