On the Coexistence of the Carbene⋯H-D Hydrogen Bond and Other Accompanying Interactions in Forty Dimers of N-Heterocyclic-Carbenes (I, IMe(2), I(i)Pr(2), I(t)Bu(2), IMes(2), IDipp(2), IAd(2); I = imidazol-2-ylidene) and Some Fundamental Proton Donors (HF, HCN, H(2)O, MeOH, NH(3))

The subject of research is forty dimers formed by imidazol-2-ylidene (I) or its derivative (IR [Formula: see text]) obtained by replacing the hydrogen atoms in both N-H bonds with larger important and popular substituents of increasing complexity (methyl = Me, iso-propyl = [Formula: see text] Pr, tert-butyl = [Formula: see text] Bu, phenyl = Ph, mesityl = Mes, 2,6-diisopropylphenyl = Dipp, 1-adamantyl = Ad) and fundamental proton donor (HD) molecules (HF, HCN, H [Formula: see text] O, MeOH, NH [Formula: see text]). While the main goal is to characterize the generally dominant C⋯H-D hydrogen bond engaging a carbene carbon atom, an equally important issue is the often omitted analysis of the role of accompanying secondary interactions. Despite the often completely different binding possibilities of the considered carbenes, and especially HD molecules, several general trends are found. Namely, for a given carbene, the dissociation energy values of the IR [Formula: see text] HD dimers increase in the following order: NH [Formula: see text] < H [Formula: see text] O < HCN ≤ MeOH ≪ HF. Importantly, it is found that, for a given HD molecule, IDipp [Formula: see text] forms the strongest dimers. This is attributed to the multiplicity of various interactions accompanying the dominant C⋯H-D hydrogen bond. It is shown that substitution of hydrogen atoms in both N-H bonds of the imidazol-2-ylidene molecule by the investigated groups leads to stronger dimers with HF, HCN, H [Formula: see text] O or MeOH. The presented results should contribute to increasing the knowledge about the carbene chemistry and the role of intermolecular interactions, including secondary ones.