Tandem copper hydride–Lewis pair catalysed reduction of carbon dioxide into formate with dihydrogen

Romero, Erik A.; Zhao, Tianxiang; Nakano, Ryo; Hu, Xingbang; Wu, Youting; Jazzar, Rodolphe; Bertrand, Guy

doi:10.1038/s41929-018-0140-3

Title: Tandem copper hydride–Lewis pair catalysed reduction of carbon dioxide into formate with dihydrogen

Journal Article · Mon Oct 01 00:00:00 EDT 2018 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-018-0140-3· OSTI ID:1594482

Romero, Erik A. ^[1]; Zhao, Tianxiang ^[2];

^[1]; Hu, Xingbang ^[2]; Wu, Youting ^[2];

^[1]; Bertrand, Guy ^[1]

Univ. of California, San Diego, CA (United States)
Nanjing Univ. (China)

The reduction of CO₂ into formic acid or its conjugate base, using dihydrogen, is an attractive process. While catalysts based on noble metals have shown high turnover numbers, the use of abundant first-row metals is underdeveloped. The key steps of the reaction are CO₂ insertion into a metal hydride and regeneration of the metal hydride with H₂, along with the concomitant production of formate. For the first step, copper is known as one of the most efficient metals, as shown by the numerous copper-catalysed carboxylation reactions, but this metal has difficulties activating H₂ to achieve the second step. In this work, we report a catalytic system involving a stable copper hydride that activates CO₂, working in tandem with a Lewis pair that heterolytically splits H₂. In this system, unprecedented turnover numbers for copper are obtained. Surprisingly, through a combination of stoichiometric and catalytic reactions, we show that classical Lewis pairs outperform frustrated Lewis pairs in this process.

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Research Organization:: Univ. of California, San Diego, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Solvay Inc., Brussels (Belgium); National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: SC0009376; 21676134; 21576129

OSTI ID:: 1594482

Journal Information:: Nature Catalysis, Vol. 1, Issue 10; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 69 works

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CCDC 1839093: Experimental Crystal Structure Determination Romero, Erik A.; Zhao, Tianxiang; Nakano, Ryo https://doi.org/10.5517/ccdc.csd.cc1zqql0 The current record is supplemented by this dataset	dataset	January 2018
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CCDC 1839095: Experimental Crystal Structure Determination Romero, Erik A.; Zhao, Tianxiang; Nakano, Ryo https://doi.org/10.5517/ccdc.csd.cc1zqqn2 The current record is supplemented by this dataset	dataset	January 2018
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