Issue 36, 2024

Direct evidence for ligand-enhanced activity of Cu(i) sites

Abstract

Little is known about the strong mediating effect of the ligand sphere and the coordination geometry on the strength and isotopologue selectivity of hydrogen adsorption on the undercoordinated copper(I) site. Here, we explore this effect using gas-phase complexes Cu+(H2O)(H2)n (with n ≤ 3) as model systems. Cu+(H2O) attracts dihydrogen (82 kJ mol1) more strongly than bare Cu+ (64 kJ mol1) does. Combining experimental and computational methods, we demonstrate a high isotopologue selectivity in dihydrogen binding to Cu+(H2O), which results from a large difference in the adsorption zero-point energies (2.8 kJ mol−1 between D2 and H2, including an anharmonic contribution of 0.4 kJ mol−1). We investigate its origins and the bond strengthening between Cu+ and H2 upon addition of a single H2O ligand. We discuss the role of the environment and the coordination geometry of the adsorption site in achieving a high selectivity and the ramifications for identifying and designing future materials for adsorptive dihydrogen isotopologue separation.

Graphical abstract: Direct evidence for ligand-enhanced activity of Cu(i) sites

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Article information

Article type
Edge Article
Submitted
10 7 2024
Accepted
09 8 2024
First published
16 8 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 14635-14643

Direct evidence for ligand-enhanced activity of Cu(I) sites

E. G. Dongmo, S. Haque, F. Kreuter, T. Wulf, J. Jin, R. Tonner-Zech, T. Heine and K. R. Asmis, Chem. Sci., 2024, 15, 14635 DOI: 10.1039/D4SC04582C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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