title: Ammonia synthesis by hydrogenolysis of titanium-nitrogen bonds using proton coupled electron transfer.
abstract: The catalytic hydrogenolysis of the titanium-amide bond in (η(5)-C5Me4SiMe3)2Ti(Cl)NH2 to yield free ammonia is described. The rhodium hydride, (η(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.
authors.affiliation: Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
authors.forename: Iraklis
authors.initials: I
authors.lastname: Pappas
authors.affiliation: Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Chirik