Nitrogen-Based Ligands Accelerate Ammonia Borane Dehydrogenation with the Shvo Catalyst

Abstract

We previously reported that quantitative poisoning, a test for homogeneous catalysis, behaves oddly in the dehydrogenation of ammonia borane (AB) by Shvo’s catalyst, whereas the “poison” 1,10-phenanthroline (phen) accelerates catalysis and apparently prevents catalyst deactivation. Thus, we proposed a protective role for phen in the catalysis. Herein we account for the mechanistic origin of this accelerated AB dehydrogenation in the presence of phen and define the relevance boundaries of our prior proposal. In so doing, we present syntheses for novel amine- and pyridine-ligated homologues of the Shvo catalyst and show their catalytic efficacy in AB dehydrogenation. These catalysts are synthetically easy to access, air stable, and rapidly release over 2 equiv of H2. The mechanisms of these reactions are also discussed.