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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 ( tBu4 PCP)IrH4 ( tBu4 PCP is [1,3-( t Bu2PCH2)-C6H3]-) in the presence of pyridine derivatives generates cationic Ir hydride complexes of the type [( tBu4 PCP)IrH(L)]+ (where L = pyridine, 2,6-lutidine, or 2-phenylpyridine). Facile deprotonation of [( tBu4 PCP)IrH(2,6-lutidine)]+ with the phosphazene base tert-butylimino-tris(pyrrolidino)phosphorane, t BuP1(pyrr), results in selective C-H activation of 1,2-difluorobenzene (1,2-DFB) solvent to generate ( tBu4 PCP)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.

SUBMITTER: Lindley BM 

PROVIDER: S-EPMC7017868 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Electrochemical C-H bond activation <i>via</i> cationic iridium hydride pincer complexes.

Lindley Brian M BM   Walden Andrew G AG   Brasacchio Ann Marie AM   Casuras Andrea A   Lease Nicholas N   Chen Chun-Hsing CH   Goldman Alan S AS   Miller Alexander J M AJM  

Chemical science 20190820 40


A C-H bond activation strategy based on electrochemical activation of a metal hydride is introduced. Electrochemical oxidation of ( <sup><i>t</i>Bu<sub>4</sub></sup> PCP)IrH<sub>4</sub> ( <sup><i>t</i>Bu<sub>4</sub></sup> PCP is [1,3-( <sup><i>t</i></sup> Bu<sub>2</sub>PCH<sub>2</sub>)-C<sub>6</sub>H<sub>3</sub>]<sup>-</sup>) in the presence of pyridine derivatives generates cationic Ir hydride complexes of the type [( <sup><i>t</i>Bu<sub>4</sub></sup> PCP)IrH(L)]<sup>+</sup> (where L = pyridine  ...[more]

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