Nature of “Hydrogen Bond” in the Diborane−Benzene Complex:  Covalent, Electrostatic, or Dispersive?

Motivated by the recent discovery of unusual “hydrogen bonding”-like interaction between a borane system and benzene molecules in a molecular crystal, we carried out quantum mechanical calculations on a model complex, diborane−benzene cluster. The aim is to understand the nature of this unique interaction, which is expected to play an essential role in this novel class of molecular crystals. As analyzed in the present study, the interaction between diborane and benzene is special in the following aspects: (1) this interaction is mostly dispersive; (2) the observed pseudodirectionality with one of the diborane bridge hydrogen directed toward the benzene centroid minimizes the van der Waals contact; and (3) in the “hydrogen bond” map, this interaction is located in a unique region, which is presently populated by a few known molecular complexes with very different chemical characteristics. It is anticipated that the results from the present analysis will provide meaningful guidance for molecular engineering with diborane−benzene as a building block and for stabilization of this and possible other hydrogen bonds by dispersive contributions.