Evidence and Governing Factors of the Radical-Ion Photoredox Catalysis
- 주제(키워드) photoredox catalysis , radical ion , deactivation , mechanism , borylation
- 주제(기타) Chemistry, Physical
- 설명문(일반) [Jeong, Dong Yeun; You, Youngmin] Ewha Womans Univ, Div Chem Engn & Mat Sci, Seoul 03760, South Korea; [Jeong, Dong Yeun; You, Youngmin] Ewha Womans Univ, Grad Program Syst Hlth Sci & Engn, Seoul 03760, South Korea; [Lee, Da Seul; Cho, Eun Jin] Chung Ang Univ, Dept Chem, Seoul 06974, South Korea; [Lee, Ha Lim] Sungkyunkwan Univ, Sch Chem Engn, Suwon 16419, South Korea; [Nah, Sanghee; Lee, Jun Yeob] Korea Basic Sci Inst KBSI, Seoul Ctr, Seoul 02841, South Korea
- 관리정보기술 faculty
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2022
- URI http://www.dcollection.net/handler/ewha/000000193055
- 본문언어 영어
- Published As https://doi.org/10.1021/acscatal.2c00763
초록/요약
Photoinduced electron transfer of a radical species provides a promising strategy for expanding the scope of photoredox catalysis. However, the mechanism underlying the radical-ion photoredox catalysis has yet been fully established. In the present research, we investigated the generation and annihilation of the key catalytic intermediate in the borylation reaction of aryl halides. To disentangle the intricate catalysis cycle, we conducted experiments using electrochemical, transient absorption and photoluminescence spectroscopy and quantum chemical calculation techniques. Our mechanistic studies provided convincing evidence that the active catalyst species is the excitedstate radical anion. We also found that the catalyst activation is retarded by multiple annihilative processes, among which the intrinsic relaxation of the excited-state radical anion of the catalyst is the most destructive. We expect these mechanistic findings will guide the future development of photoredox catalysis of radical species.
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