Reversible Interfacial Hydride Transfer as a Complementary Tool To Measure Molecular Hydricity

Chung, Hye Won; Wang, Hai-Xu; Desai, Sai Puneet; Müller, Andressa V.; Sena, Sebastian; Glusac, Ksenija D.; Concepcion, Javier J.; Surendranath, Yogesh

doi:10.1021/jacs.5c09582

Reversible Interfacial Hydride Transfer as a Complementary Tool To Measure Molecular Hydricity

Journal Article · Mon Sep 29 00:00:00 UTC 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5c09582· OSTI ID:3001461

Chung, Hye Won ^[1]; Wang, Hai-Xu ^[1]; ^[2]; Müller, Andressa V. ^[2]; Sena, Sebastian ^[3]; ^[3]; ^[2]; ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Univ. of Illinois, Chicago, IL (United States)

Hydride transfer is an essential elementary reaction across the chemical value chain, but there are limited methods available for quantifying thermodynamic hydricity (ΔG_H-), particularly among main group reagents. Herein, we exploit facile H₂ activation and reversible hydride transfer from a metal surface to a molecular reagent, the net hydrogen reduction reaction (HRR), to develop a potentiometric method for quantifying ΔG_H- of main group reagents recalcitrant to conventional methods. HRR potentiometry is first validated with a benzimidazole-based hydride donor and then applied to uncover the impact of the reaction environment on hydricity. For a benzimidazole-based hydride donor, HRR equilibrium potentials are roughly invariant across solvents, indicating that the solvent dependence of its hydricity largely reflects the differential solvation of H^- across media. For formate, HRR potentials and corresponding hydricities depend strongly on water content. Additionally, for borohydrides, HRR potentiometry reveals that effective hydricity values are strongly influenced by Lewis acid-base adduct formation with the hydride acceptor but are minimally influenced by the countercation. Together with these studies, the advantages, limitations, and practical considerations of the HRR potentiometry method are discussed, highlighting the power of this methodology as a complementary tool to measure molecular hydricity.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357; SC0012704; SC0021173

OSTI ID:: 3001461

Report Number(s):: BNL--229102-2025-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 40 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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