期刊
ACS CATALYSIS
卷 9, 期 1, 页码 200-204出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.8b04326
关键词
charge-transfer; cobalt catalysis; cycloaddition; light-driven; photoredox
资金
- Catalysis Collaboratory for Light-activated Earth Abundant Reagents (CCLEAR) - National Science Foundation
- Environmental Protection Agency through the Network for Sustainable Molecular Design and Synthesis program [NSFCHE-1339674]
- National Institute of General Medical Sciences [GM125206]
- Societe de Chimie Industrielle
Photoredox catalysis can be used to manipulate the redox state of a transition metal complex leading to the desired reactivity. While powerful, obviating the role of the second catalyst would be attractive from the perspective of simplifying the protocol and using visible light to uncover unexpected, enabling reactivity. Herein we report that Co-acetylides, formed in situ, are photoactive complexes that undergo ligand-to-metal charge transfer using visible light. The net transformation uses air-stable Co(II) complexes as precatalysts and induces Co(I) chemistry. The acetylide is an electron reservoir forming the Co(I) but accepting the electron back at the end of the catalytic cycle. The electronic nature of the acetylide leads to either on-off behavior or simply initiates catalysis, depending on electronics.
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