Abstract

Ammonia borane (AB) is a promising hydrogen storage material due to its high hydrogen storage capacity. AB dehydrogenation can be facilitated by metal-halide (MCl2) catalysis. Here, we have elucidated the dehydrogenation mechanism of AB via MCl2 catalysis using ab initio calculations. In contrast to a typical electrophilic substitution (SE) reaction occurring at a carbon atom, the nitrogen atom in AB serves as the reaction center for the SE reaction with the boron moiety as the leaving group when MCl2 approaches AB. In addition, the SE2 backside reaction is favored as the initial step for the dehydrogenation of AB by MCl2. This work paves the way for the use of a new reaction in the field of BN chemistry.