The ability of substituted boranes, XnBH3−n, to form stable complexes with the hydrogen molecule is analyzed by making use of computational chemistry and local reactivity parameters. In these complexes, the hydrogen molecule acts as a Lewis base while the borane moiety is the Lewis acid. Electronegative groups (X = CF3, F, OH) are selected to increase the acidity of the borane and it is found that the energetic stability of the complexes is only increased for the trifluoromethyl-substituted Lewis acids, at the MP2/6-311++g(3df, 3pd) level. It is also found that the BLYP density functional underestimates the adduct stability of these species. On the other hand, fluoroboranes and hydroxyboranes do not form donor–acceptor adducts with the hydrogen molecule; instead, we find weakly bounded van der Waals complexes. Additional features on the intrinsic reactivity of boranes are analyzed with the molecular electrostatic potential and the acceptor Fukui function. The nature of the interaction among the boranes and the hydrogen molecule is explored by using the topological analysis of the electron density through the Bader's Atoms-in-Molecules theory. © 2012 Wiley Periodicals, Inc.