The catalytic hydrogenolysis of the titaniumamide bond in (eta(5)-C5Me4SiMe3)(2)Ti(Cl)NH2 to yield free ammonia is described. The rhodium hydride, (eta(5)-C5Me5)(py-Ph)RhH (py-Ph = 2-phenylpyridine), serves as the catalyst and promotes N-H bond formation via hydrogen atom transfer. The N-H bond dissociation free energies of ammonia ligands have also been determined for titanocene and zirconocene complexes and reveal a stark dependence on metal identity and oxidation state. In all cases, the N-H BDFEs of coordinated NH3 decreases by >40 kcal/mol from the value in the free gas phase molecule.