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Zall CM, Linehan JC, Appel AM. Triphosphine-Ligated Copper Hydrides for CO2 Hydrogenation: Structure, Reactivity, and Thermodynamic Studies. J Am Chem Soc. 2016;138(31):9968-77doi: 10.1021/jacs.6b05349.
Zall, C. M., Linehan, J. C., & Appel, A. M. (2016). Triphosphine-Ligated Copper Hydrides for CO2 Hydrogenation: Structure, Reactivity, and Thermodynamic Studies. Journal of the American Chemical Society, 138(31), 9968-77. https://doi.org/10.1021/jacs.6b05349
Zall, Christopher M, et al. "Triphosphine-Ligated Copper Hydrides for CO2 Hydrogenation: Structure, Reactivity, and Thermodynamic Studies." Journal of the American Chemical Society vol. 138,31 (2016): 9968-77. doi: https://doi.org/10.1021/jacs.6b05349
Zall CM, Linehan JC, Appel AM. Triphosphine-Ligated Copper Hydrides for CO2 Hydrogenation: Structure, Reactivity, and Thermodynamic Studies. J Am Chem Soc. 2016 Aug 10;138(31):9968-77. doi: 10.1021/jacs.6b05349. Epub 2016 Aug 01. PMID: 27434540.
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J Am Chem Soc. 2016 Aug 10;138(31):9968-77. doi: 10.1021/jacs.6b05349. Epub 2016 Aug 01.

Triphosphine-Ligated Copper Hydrides for CO2 Hydrogenation: Structure, Reactivity, and Thermodynamic Studies.

Journal of the American Chemical Society

Christopher M Zall, John C Linehan, Aaron M Appel

Affiliations

  1. Pacific Northwest National Laboratory , Richland, Washington 99352, United States.

PMID: 27434540 DOI: 10.1021/jacs.6b05349

Abstract

The copper(I) triphosphine complex LCu(MeCN)PF6 (L = 1,1,1-tris(diphenylphosphinomethyl)ethane), which we recently demonstrated is an active catalyst precursor for hydrogenation of CO2 to formate, reacts with H2 in the presence of a base to form a cationic dicopper hydride, [(LCu)2H]PF6. [(LCu)2H](+) is also an active precursor for catalytic CO2 hydrogenation, with equivalent activity to that of LCu(MeCN)(+), and therefore may be a relevant catalytic intermediate. The thermodynamic hydricity of [(LCu)2H](+) was determined to be 41.0 kcal/mol by measuring the equilibrium constant for this reaction using three different bases. [(LCu)2H](+) and the previously reported dimer (LCuH)2 can be synthesized by the reaction of LCu(MeCN)(+) with 0.5 and 1 equiv of KB(O(i)Pr)3H, respectively. The solid-state structure of [(LCu)2H](+) shows threefold symmetry about a linear Cu-H-Cu axis and significant steric strain imposed by bringing two LCu(+) units together around the small hydride ligand. [(LCu)2H](+) reacts stoichiometrically with CO2 to generate the formate complex LCuO2CH and the solvento complex LCu(MeCN)(+). The rate of the stoichiometric reaction between [(LCu)2H](+) and CO2 is dramatically increased in the presence of bases that coordinate strongly to the copper center, e.g. DBU and TMG. In the absence of CO2, the addition of a large excess of DBU to [(LCu)2H](+) results in an equilibrium that forms LCu(DBU)(+) and also presumably the mononuclear hydride LCuH, which is not directly observed. Due to the significantly enhanced CO2 reactivity of [(LCu)2H](+) under these catalytically relevant conditions, LCuH is proposed to be the catalytically active metal hydride.

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