期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 -, 期 -, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202216511
关键词
Alkyne Semihydrogenation; Electron-Proton Transfer; Monovalent Nickel; Photocatalysis; Single-Atom Catalysis
Prospects in light-driven water activation have led to rapid progress in hydrogenation reactions. In this study, a Ni2+-N-4 site built on carbon nitride was used for catalyzing the semihydrogenation of alkynes with water providing protons, powered by visible-light irradiation. Importantly, this photocatalytic approach enabled the production of diverse deuterated alkenes in D2O with excellent deuterium incorporation.
Prospects in light-driven water activation have prompted rapid progress in hydrogenation reactions. We describe a Ni2+-N-4 site built on carbon nitride for catalyzed semihydrogenation of alkynes, with water supplying protons, powered by visible-light irradiation. Importantly, the photocatalytic approach developed here enabled access to diverse deuterated alkenes in D2O with excellent deuterium incorporation. Under visible-light irradiation, evolution of a four-coordinate Ni2+ species into a three-coordinate Ni+ species was spectroscopically identified. In combination with theoretical calculations, the photo-evolved Ni+ is posited as HO-Ni+-N-2 with an uncoordinated, protonated pyridinic nitrogen, formed by coupled Ni2+ reduction and water dissociation. The paired Ni-N prompts hydrogen liberation from water, and it renders desorption of alkene preferred over further hydrogenation to alkane, ensuring excellent semihydrogenation selectivity.
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