Year: 2024
Type: article
Abstract: Herein, we dismiss a recent proposal by Civiš, Hobza, and co-workers to modify the IUPAC definition of hydrogen bonds in order to expand the scope from protonic Y–Hδ+ to hydridic Y–Hδ− hydrogen-bond donor fragments [J. Am. Chem. Soc. 2023, 145, 8550]. Based on accurate Kohn–Sham molecular orbital (KS-MO) analyses, we falsify the conclusion that interactions involving protonic and hydridic hydrogens are both hydrogen bonds; they are not. Instead, our quantitative KS-MO, energy decomposition, and Voronoi deformation density analyses reveal two fundamentally different bonding mechanisms for protonic Y–Hδ+ and hydridic Y–Hδ− fragments which go with charge transfer in opposite directions. On one hand, we confirm the IUPAC definition for regular hydrogen bonds in the case of protonic Y–Hδ+ fragments. On the other hand, complexes involving Y–Hδ− fragments are, in fact, acceptors in other well-known families of Lewis-acid/base interactions, such as halogen bonds, chalcogen bonds, and pnictogen bonds. These mechanisms lead to the same spectroscopic phenomenon in both the Y–Hδ+ and Y–Hδ− fragments, that is, the redshift in the Y–H stretching frequency, which is, thus, not an exclusive indicator for hydrogen bonding.
DOI: 10.1021/jacs.4c07821
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4402193083