"Hydridic Hydrogen-Bond Donors" Are Not Hydrogen-Bond Donors

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-H^δ+ to hydridic Y-H^δ- 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-H^δ+ and hydridic Y-H^δ- 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-H^δ+ fragments. On the other hand, complexes involving Y-H^δ- 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-H^δ+ and Y-H^δ- fragments, that is, the redshift in the Y-H stretching frequency, which is, thus, not an exclusive indicator for hydrogen bonding.