Zott, Michael D. and Canestraight, Virginia M. and Peters, Jonas C. (2022) Mechanism of a Luminescent Dicopper System That Facilitates Electrophotochemical Coupling of Benzyl Chlorides via a Strongly Reducing Excited State. ACS Catalysis, 12 (17). pp. 10781-10786. ISSN 2155-5435. doi:10.1021/acscatal.2c03215. https://resolver.caltech.edu/CaltechAUTHORS:20221017-10817000.2
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Abstract
Photochemical radical generation has become a modern staple in chemical synthesis and methodology. Herein, we detail the photochemistry of a highly reducing, highly luminescent dicopper system [Cu₂] (Eₒₓ* ≈ −2.7 V vs SCE; τₒ ≈ 10 μs) within the context of a model reaction: single-electron reduction of benzyl chlorides. The dicopper system is mechanistically well defined. As we show, it is the [Cu₂]* excited state that serves as the outer-sphere photoreductant of benzyl chloride substrates; the ground-state oxidized byproduct, [Cu₂]⁺, is electrochemically recycled, demonstrating a catalytic electrophotochemical C–C coupling process.
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| Additional Information: | The authors are grateful to the National Institutes of Health (NIGMS: R01-109194) for support of this research. M.D.Z. acknowledges the Resnick Sustainability Institute at Caltech and the National Science Foundation (DGE-1745301) for support via Graduate Fellowships. V.M.C. acknowledges the John Stauffer Charitable Trust and Caltech’s Summer Undergraduate Research Fellowships program for summer research funding. The Beckman Institute Laser Resource Center and Jay R. Winkler are acknowledged for providing support with steady-state and time-resolved luminescence experiments. We acknowledge Dr. Joseph Derosa for insightful discussions. | ||||||||||||
| Group: | Resnick Sustainability Institute | ||||||||||||
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| Issue or Number: | 17 | ||||||||||||
| DOI: | 10.1021/acscatal.2c03215 | ||||||||||||
| Record Number: | CaltechAUTHORS:20221017-10817000.2 | ||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20221017-10817000.2 | ||||||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
| ID Code: | 117444 | ||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||
| Deposited By: | Research Services Depository | ||||||||||||
| Deposited On: | 20 Oct 2022 17:00 | ||||||||||||
| Last Modified: | 20 Oct 2022 17:00 |
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