Magnesocenophane‐Catalyzed Amine Borane Dehydrocoupling

The Lewis acidities of a series of [n]magnesocenophanes (1 a–d) have been investigated computationally and found to be a function of the tilt of the cyclopentadienyl moieties. Their catalytic abilities in amine borane dehydrogenation/dehydrocoupling reactions have been probed, and C[1]magnesocenophane (1 a) has been shown to effectively catalyze the dehydrogenation/dehydrocoupling of dimethylamine borane (2 a) and diisopropylamine borane (2 b) under ambient conditions. Furthermore, the mechanism of the reaction with 2 a has been investigated experimentally and computationally, and the results imply a ligand‐assisted mechanism involving stepwise proton and hydride transfer, with dimethylaminoborane as the key intermediate.