This report explores the potential of the unconventional hydrogen bonds between the hydridic hydrogens in X-BH3- (X=H, CN) and traditional OH or NH proton donors (dihydrogen bonds) to serve as preorganizing interactions for the topochemical assembly of covalent materials. Evidence for such topochemical control in the reaction B-H×××H-X ® B-X + H2 was obtained in studies of the solid state structures and reactivities of N-[2-(6-aminopyridyl)]-acetamidine

The first mechanistic investigation of a topochemical dihydrogen to covalent bonding conversion is presented. Solid state decomposition of the LiBH4×TEA (TEA = triethanolamine) dihydrogen-bonded complex into a covalent material was studied using 11B solid state MAS NMR, FT-IR, XRD, and optical microscopy. The majority of this solid state reaction occurs by nucleation and two-dimensional growth of the covalent product nuclei. Variable temperature