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

doi:10.1039/c9sc03076j

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

School of Arts and Sciences, Chemistry & Chemical Biology

Rutgers, The State University

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

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 language	American English
Pages (from-to)	9326-9330
Number of pages	5
Journal	Chemical Science
Volume	10
Issue number	40
DOIs	https://doi.org/10.1039/c9sc03076j
State	Published - 2019

ASJC Scopus subject areas

General Chemistry

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@article{13f7049585534261b9dd6cabfdcaa2dd,

title = "Electrochemical C-H bond activation: Via cationic iridium hydride pincer complexes",

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.",

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

note = "Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c9sc03076j",

language = "American English",

volume = "10",

pages = "9326--9330",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "40",

}

TY - JOUR

T1 - Electrochemical C-H bond activation

T2 - Via cationic iridium hydride pincer complexes

AU - Lindley, Brian M.

AU - Walden, Andrew G.

AU - Brasacchio, Ann Marie

AU - Casuras, Andrea

AU - Lease, Nicholas

AU - Chen, Chun Hsing

AU - Goldman, Alan S.

AU - Miller, Alexander J.M.

PY - 2019

Y1 - 2019

N2 - 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.

AB - 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.

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U2 - 10.1039/c9sc03076j

DO - 10.1039/c9sc03076j

M3 - Article

SN - 2041-6520

VL - 10

SP - 9326

EP - 9330

JO - Chemical Science

JF - Chemical Science

IS - 40

ER -

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

Abstract

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