Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

198 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)13318-13322
Number of pages5
JournalAngewandte Chemie - International Edition
Volume58
Issue number38
DOIs
Publication statusPublished - 16 Sept 2019
Externally publishedYes

Keywords

  • C−H functionalization
  • Electrophotocatalysis
  • oxidation
  • radical dication
  • trisaminocyclopropenium ion

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Huang, H., Strater, Z. M., Rauch, M., Shee, J., Sisto, T. J., Nuckolls, C., & Lambert, T. H. (2019). Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication. Angewandte Chemie - International Edition, 58(38), 13318-13322. https://doi.org/10.1002/anie.201906381