title: The roles of dihydrogen bonds in amine borane chemistry.
abstract: A dihydrogen bond (DHB) is an electrostatic interaction between a protonic hydrogen and a hydridic hydrogen. Over the past two decades, researchers have made significant progress in the identification and characterization of DHBs and their properties. In comparison with conventional hydrogen bonds (HBs), which have been widely used in catalysis, molecular recognition, crystal engineering, and supramolecular synthesis, chemists have only applied DHBs in very limited ways. Considering that DHBs and conventional HBs have comparable strength, DHBs could be more widely applied in chemistry. Over the past several years, we have explored the impact of DHBs on amine borane chemistry and the syntheses and characterization of amine boranes and ammoniated metal borohydrides for hydrogen storage. Through systematic computational and experimental investigations, we found that DHBs play a dominant role in dictating the reaction pathways (and thus different products) of amine boranes where oppositely charged hydrogens coexist for DHB formation. Through careful experiments, we observed, for the first time, a long-postulated reaction intermediate, ammonia diborane (AaDB), whose behavior is essential to mechanistic understanding of the formation of the diammoniate of diborane (DADB) in the reaction of ammonia (NH3) with tetrahydrofuran borane (THF·BH3). The formation of DADB has puzzled the boron chemistry community for decades. Mechanistic insight enabled us to develop facile syntheses of aminodiborane (ADB), ammonia borane (AB), DADB, and an inorganic butane analog NH3BH2NH2BH3 (DDAB). Our examples, together with those in the literature, reinforce the fact that DHB formation and subsequent molecular hydrogen elimination are a viable approach for creating new covalent bonds and synthesizing new materials. We also review the strong effects of DHBs on the stability of conformers and the hydrogen desorption temperatures of boron-nitrogen compounds. We hope that this Account will encourage further applications of DHBs in molecular recognition, host-guest chemistry, crystal engineering, supramolecular chemistry, molecular self-assembly, chemical kinetics, and the syntheses of new advanced materials.
authors.affiliation: School of Chemistry and Chemical Engineering, Henan Normal University , Xinxiang, Henan 453007, China.
authors.forename: Xuenian
authors.initials: X
authors.lastname: Chen
authors.forename: Ji-Cheng
authors.initials: JC
authors.lastname: Zhao
authors.forename: Sheldon G
authors.initials: SG
authors.lastname: Shore