Catalytic Ammonia Oxidation to Dinitrogen by a Nickel Complex

We report a nickel complex for catalytic oxidation of ammonia to dinitrogen under ambient conditions. Using the aryloxyl radical 2,4,6-tri-tert-butylphenoxyl ((Bu3ArO center dot)-Bu-t) as a H atom acceptor to cleave the N-H bond of a coordinated NH3 ligand up to 56 equiv of N-2 per Ni center can be generated. Employing the N-oxyl radical 2,2,6,6-(tetramethylpiperidin-1-yl)oxyl (TEMPO center dot) as the H-atom acceptor, up to 15 equiv of N-2 per Ni center are formed. A bridging Ni-hydrazine product identified by isotopic nitrogen (N-15) studies and supported by computational models indicates the N-N bond forming step occurs by bimetallic homocoupling of two paramagnetic [Ni]-NH2 fragments. Ni-mediated hydrazine disproportionation to N-2 and NH3 completes the catalytic cycle.