Synthesis and Reactivity of Fe(II) Complexes Containing Cis Ammonia Ligands

The development of earth-abundant transition-metal complexes for electrocatalytic ammonia oxidation is needed to facilitate a renewable energy economy. Important to this goal is a fundamental understanding of how ammonia binds to complexes as a function of ligand geometry and electronic effects. We report the synthesis and characterization of a series of Fe(II)-NH3 complexes supported by tetradentate, facially binding ligands with a combination of pyridine and N-heterocyclic carbene donors. Electronic modification of the supporting ligand led to significant shifts in the Fe-III/II potential and variations in NH bond acidities. Finally, investigations of ammonia oxidation by cyclic voltammetry, controlled potential bulk electrolysis, and through addition of stoichiometric organic radicals, TEMPO and (ArO center dot)-Ar-tBu3 are reported. No catalytic oxidation of NH3 to N-2 was observed, and N-15(2) was detected only in reactions with (ArO center dot)-Ar-tBu3.