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/ange.201906381

Title: Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication

Journal Article · 01 August 2019 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201906381 · OSTI ID:1546094

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

^[3]

Department of Chemistry and Chemical Biology Cornell University Ithaca NY 14853 USA
Department of Chemistry Columbia University New York NY 10027 USA
Department of Chemistry and Chemical Biology Cornell University Ithaca NY 14853 USA, Department of Chemistry Columbia University New York NY 10027 USA

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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Sponsoring Organization:: USDOE

OSTI ID:: 1546094

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 38 Vol. 131; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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