Issue 43, 2023

Unravelling strong temperature-dependence of JHD in transition metal hydrides: solvation and non-covalent interactions versus temperature-elastic H–H bonds

Abstract

A number of transition metal hydrides reveal intriguing temperature-dependent JHD in their deuterated derivatives and possibly the temperature dependent hydrogen–hydrogen distance (r(H–H)) as well. Previously, theoretical studies rationalized JHD and r(H–H) changes in such compounds through a “temperature-elastic” structure model with a significant population of vibrational states in an anharmonic potential. Based on the first variable temperature neutron diffraction study of a relevant complex, (p-H-POCOP)IrH2, observation of its elusive counterpart with longer r(H–H), crystallized as an adduct with C6F5I, and thorough spectroscopic and computational study, we argue that the model involving isomeric species in solution at least in some cases is more relevant. The existence of such isomers is enabled or enhanced by solvation and weak non-covalent interactions with solvent, such as halogen or dihydrogen bonds. “Non-classical” hydrides with r(H–H) ≈ 1.0–1.6 Å are especially sensitive to the above-mentioned factors.

Graphical abstract: Unravelling strong temperature-dependence of JHD in transition metal hydrides: solvation and non-covalent interactions versus temperature-elastic H–H bonds

Supplementary files

Article information

Article type
Edge Article
Submitted
11 Aug 2023
Accepted
12 Oct 2023
First published
13 Oct 2023
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., 2023,14, 12308-12320

Unravelling strong temperature-dependence of JHD in transition metal hydrides: solvation and non-covalent interactions versus temperature-elastic H–H bonds

A. V. Polukeev, S. C. Capelli and O. F. Wendt, Chem. Sci., 2023, 14, 12308 DOI: 10.1039/D3SC04197B

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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