Electrochemical C-H bond activation: Via cationic iridium hydride pincer complexes

Brian M. Lindley, Andrew G. Walden, Ann Marie Brasacchio, Andrea Casuras, Nicholas Lease, Chun Hsing Chen, Alan S. Goldman, Alexander J.M. Miller

Research output: Contribution to journalArticle

Abstract

A C-H bond activation strategy based on electrochemical activation of a metal hydride is introduced. Electrochemical oxidation of (tBu4PCP)IrH4 (tBu4PCP is [1,3-(tBu2PCH2)-C6H3]-) in the presence of pyridine derivatives generates cationic Ir hydride complexes of the type [(tBu4PCP)IrH(L)]+ (where L = pyridine, 2,6-lutidine, or 2-phenylpyridine). Facile deprotonation of [(tBu4PCP)IrH(2,6-lutidine)]+ with the phosphazene base tert-butylimino-tris(pyrrolidino)phosphorane, tBuP1(pyrr), results in selective C-H activation of 1,2-difluorobenzene (1,2-DFB) solvent to generate (tBu4PCP)Ir(H)(2,3-C6F2H3). The overall electrochemical C-H activation reaction proceeds at room temperature without need for chemical activation by a sacrificial alkene hydrogen acceptor. This rare example of undirected electrochemical C-H activation holds promise for the development of future catalytic processes.

Original languageEnglish
Pages (from-to)9326-9330
Number of pages5
JournalChemical Science
Volume10
Issue number40
DOIs
Publication statusPublished - Jan 1 2019

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Iridium
Hydrides
Chemical activation
Hydrogen
Phosphoranes
Deprotonation
Electrochemical oxidation
Alkenes
Metals
Derivatives

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Lindley, B. M., Walden, A. G., Brasacchio, A. M., Casuras, A., Lease, N., Chen, C. H., ... Miller, A. J. M. (2019). Electrochemical C-H bond activation: Via cationic iridium hydride pincer complexes. Chemical Science, 10(40), 9326-9330. https://doi.org/10.1039/c9sc03076j

Electrochemical C-H bond activation : Via cationic iridium hydride pincer complexes. / Lindley, Brian M.; Walden, Andrew G.; Brasacchio, Ann Marie; Casuras, Andrea; Lease, Nicholas; Chen, Chun Hsing; Goldman, Alan S.; Miller, Alexander J.M.

In: Chemical Science, Vol. 10, No. 40, 01.01.2019, p. 9326-9330.

Research output: Contribution to journalArticle

Lindley, BM, Walden, AG, Brasacchio, AM, Casuras, A, Lease, N, Chen, CH, Goldman, AS & Miller, AJM 2019, 'Electrochemical C-H bond activation: Via cationic iridium hydride pincer complexes', Chemical Science, vol. 10, no. 40, pp. 9326-9330. https://doi.org/10.1039/c9sc03076j
Lindley BM, Walden AG, Brasacchio AM, Casuras A, Lease N, Chen CH et al. Electrochemical C-H bond activation: Via cationic iridium hydride pincer complexes. Chemical Science. 2019 Jan 1;10(40):9326-9330. https://doi.org/10.1039/c9sc03076j
Lindley, Brian M. ; Walden, Andrew G. ; Brasacchio, Ann Marie ; Casuras, Andrea ; Lease, Nicholas ; Chen, Chun Hsing ; Goldman, Alan S. ; Miller, Alexander J.M. / Electrochemical C-H bond activation : Via cationic iridium hydride pincer complexes. In: Chemical Science. 2019 ; Vol. 10, No. 40. pp. 9326-9330.
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