Single-Atom Nickel on Carbon Nitride Photocatalyst Achieves Semihydrogenation of Alkynes with Water Protons via Monovalent Nickel
© 2023 Wiley-VCH GmbH..
Prospects in light-driven water activation have prompted rapid progress in hydrogenation reactions. We describe a Ni2+ -N4 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 D2 O 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+ -N2 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.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:62 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - 62(2023), 9 vom: 20. Feb., Seite e202216511 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Jia, Tongtong [VerfasserIn] |
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| Links: |
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| Themen: |
Alkyne Semihydrogenation |
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| Anmerkungen: |
Date Completed 17.02.2023 Date Revised 17.02.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/anie.202216511 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM351365125 |
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| 500 | |a Date Revised 17.02.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2023 Wiley-VCH GmbH. | ||
| 520 | |a Prospects in light-driven water activation have prompted rapid progress in hydrogenation reactions. We describe a Ni2+ -N4 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 D2 O 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+ -N2 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 | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Alkyne Semihydrogenation | |
| 650 | 4 | |a Electron-Proton Transfer | |
| 650 | 4 | |a Monovalent Nickel | |
| 650 | 4 | |a Photocatalysis | |
| 650 | 4 | |a Single-Atom Catalysis | |
| 700 | 1 | |a Meng, Di |e verfasserin |4 aut | |
| 700 | 1 | |a Duan, Ran |e verfasserin |4 aut | |
| 700 | 1 | |a Ji, Hongwei |e verfasserin |4 aut | |
| 700 | 1 | |a Sheng, Hua |e verfasserin |4 aut | |
| 700 | 1 | |a Chen, Chuncheng |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Jikun |e verfasserin |4 aut | |
| 700 | 1 | |a Song, Wenjing |e verfasserin |4 aut | |
| 700 | 1 | |a Zhao, Jincai |e verfasserin |4 aut | |
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