Spontaneous N2 formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia.

The electrochemical conversion of ammonia to dinitrogen in a direct ammonia fuel cell (DAFC) is a necessary technology for the realization of a nitrogen economy. Previous efforts to catalyse this reaction with molecular complexes required the addition of exogenous oxidizing reagents or application of potentials greater than the thermodynamic potential for the oxygen reduction reaction-the cathodic process of a DAFC. We report a stable metal-metal bonded diruthenium complex that spontaneously produces dinitrogen from ammonia under ambient conditions. The resulting reduced diruthenium material can be reoxidized with oxygen for subsequent reactions with ammonia, demonstrating its ability to spontaneously promote both half-reactions necessary for a DAFC. The diruthenium complex also acts as a redox mediator for the electrocatalytic oxidation of ammonia to dinitrogen at potentials as low as -255 mV versus Fc0/+ and operates below the oxygen reduction reaction potential in alkaline conditions, thus achieving a thermodynamic viability relevant for the future development of DAFCs.

Coordination of Hydrogen Peroxide with Late-Transition-Metal Sulfonamido Complexes.

Adducts of hydrogen peroxide and transition metals have been implicated as intermediates in biological and industrial processes but have only recently been observed. Therefore, knowledge of how hydrogen peroxide interacts with transition metals is extremely limited. Herein, we report the synthesis of H2O2 complexes of cobalt, nickel, and copper supported by sulfonamido ligands with second-sphere hydrogen bonding. Binding constant and decay kinetics are reported for four new M(H2O2) adducts, providing a foundation for future studies in H2O2 coordination and oxidation catalysis.

Hydrogen Peroxide Coordination to Cobalt(II) Facilitated by Second-Sphere Hydrogen Bonding.

M(H2 O2 ) adducts have been postulated as intermediates in biological and industrial processes; however, only one observable M(H2 O2 ) adduct has been reported, where M is redox-inactive zinc. Herein, direct solution-phase detection of an M(H2 O2 ) adduct with a redox-active metal, cobalt(II), is described. This Co(II) (H2 O2 ) compound is made observable by incorporating second-sphere hydrogen-bonding interactions between bound H2 O2 and the supporting ligand, a trianionic trisulfonamido ligand. Thermodynamics of H2 O2 binding and decay kinetics of the Co(II) (H2 O2 ) species are described, as well as the reaction of this Co(II) (H2 O2 ) species with Group 2 cations.

Hydrogen Peroxide Complex of Zinc.

Metal(H2O2) complexes have been implicated in kinetic and computational studies but have never been observed. Accordingly, H2O2 has been described as a very weak ligand. We report the first metal(H2O2) adduct, which is made possible by incorporating intramolecular hydrogen-bonding interactions with bound H2O2. This Zn(II)(H2O2) complex decays in solution by a second-order process that is slow enough to enable characterization of this species by X-ray crystallography. This report speaks to the intermediacy of metal(H2O2) adducts in chemistry and biology and opens the door to exploration of these species in oxidation catalysis.