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Photocatalytic Activity of Diverse Organic Radical Anions: Catalyst Discovery Enables Cleavage of Strong C(sp2)–N and C(sp2)–O Bonds

preprint
submitted on 01.06.2021, 13:48 and posted on 02.06.2021, 11:25 by Colleen Chernowsky, Alyah Chmiel, Zachary Wickens

Herein, we leverage electrochemistry to examine the photocatalytic activity of a range of structurally diverse persistent radical anions and find that many are effective electrophotocatalysts. These studies uncover a new electron-primed photoredox catalyst capable of promoting the reductive cleavage of strong C(sp2)–N and C(sp2)–O bonds even when reduction potentials hundreds of mV more negative than Li0 are required. We illustrated several examples of the synthetic utility of these deeply reducing but otherwise safe and mild catalytic conditions. Finally, we employed electrochemical current measurements to perform a reaction progress kinetic analysis that revealed that the improved activity of this new catalyst was a consequence of an enhanced stability profile.

Funding

This material is based upon work supported by the National Science Foundation under Grant No. (2047108).

Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for partial funding of this research (60677-DNI1)

Spectroscopic instrumentation was supported by a generous gift from Paul. J. and Margaret M. Bender, NSF (CHE-1048642), and NIH (1S10 OD020022-1).

History

Email Address of Submitting Author

wickens@wisc.edu

Institution

University of Wisconsin–Wisconsin

Country

USA

ORCID For Submitting Author

0000-0002-5733-5288

Declaration of Conflict of Interest

none