The catalytic dehydrogenation of ammonia and amine-boranes by a dimethylxanthene-derived frustrated Lewis pair is described. Turnover is facilitated on a thermodynamic basis by the ready release of H-2 from the weakly basic PPh2-containing system. In situ NMR studies and the isolation of intermediates from stoichiometric reactions support a mechanism initiated by B-H activation, followed by end-growth BN coupling involving the terminal NH bond of the bound BN fragment and a BH bond of the incoming borane monomer.