Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication

Huang, He; Strater, Zack M.; Rauch, Michael; Shee, James; Sisto, Thomas J.; Nuckolls, Colin; Lambert, Tristan H.

doi:10.1002/anie.201906381

Title: Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication

Journal Article · Mon Jul 15 00:00:00 EDT 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201906381· OSTI ID:1613231

Huang, He ^[1]; Strater, Zack M. ^[2]; Rauch, Michael ^[2]; Shee, James ^[2]; Sisto, Thomas J. ^[2]; Nuckolls, Colin ^[2];

^[3]

Cornell Univ., Ithaca, NY (United States)
Columbia Univ., New York, NY (United States)
Cornell Univ., Ithaca, NY (United States); Columbia Univ., New York, NY (United States)

Abstract Visible‐light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions. Here, these two modalities are combined in an electrophotocatalytic oxidation platform. This chemistry employs a trisaminocyclopropenium (TAC) ion catalyst, which is electrochemically oxidized to form a cyclopropenium radical dication intermediate. The radical dication undergoes photoexcitation with visible light to produce an excited‐state species with oxidizing power (3.33 V vs. SCE) sufficient to oxidize benzene and halogenated benzenes via single‐electron transfer (SET), resulting in C−H/N−H coupling with azoles. A rationale for the strongly oxidizing behavior of the photoexcited species is provided, while the stability of the catalyst is rationalized by a particular conformation of the cis ‐2,6‐dimethylpiperidine moieties.

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Research Organization:: Columbia Univ., New York, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Institutes of Health (NIH); National Science Foundation (NSF)

Grant/Contract Number:: SC0019440; R35 GM127135; DGE-1644869; CHE-0619638

OSTI ID:: 1613231

Alternate ID(s):: OSTI ID: 1546103

Journal Information:: Angewandte Chemie (International Edition), Vol. 58, Issue 38; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 148 works

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Merging Photocatalysis with Electrochemistry: The Dawn of a new Alliance in Organic Synthesis Capaldo, Luca; Quadri, Lorenzo L.; Ravelli, Davide Angewandte Chemie International Edition, Vol. 58, Issue 49 https://doi.org/10.1002/anie.201910348	journal	December 2019
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Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols Zhang, Wen; Carpenter, Keith L.; Lin, Song Angewandte Chemie, Vol. 132, Issue 1 https://doi.org/10.1002/ange.201910300	journal	November 2019
Electrophotocatalytic S _N Ar Reactions of Unactivated Aryl Fluorides at Ambient Temperature and Without Base Huang, He; Lambert, Tristan H. Angewandte Chemie International Edition, Vol. 59, Issue 2 https://doi.org/10.1002/anie.201909983	journal	January 2020
Electrophotocatalysis: Cyclic Voltammetry as an Analytical Tool Costentin, Cyrille; Fortage, Jérôme; Collomb, Marie-Noëlle The Journal of Physical Chemistry Letters, Vol. 11, Issue 15 https://doi.org/10.1021/acs.jpclett.0c01662	journal	July 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
C−H functionalization
electrophotocatalysis
oxidation
radical dication
trisaminocyclopropenium ion

Title: Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication

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