Computational Analysis of Low Overpotential Ammonia Oxidation by Metal-Metal Bonded Ruthenium Catalysts, and Predictions for Related Osmium Catalysts.

The catalyzed electrochemical oxidation of ammonia to nitrogen (AOR) is an important fuel-cell half-reaction that underpins a future nitrogen-based energy economy. Our laboratory has reported spontaneous chemical and electrochemical oxidation of ammonia to dinitrogen via reaction of ammonia with the metal-metal bonded diruthenium complex Ru2(chp)4OTf (chp- = 2-chloro-6-hydroxypyridinate, TfO- = trifluoromethanesulfonate). This complex facilitates electrocatalytic ammonia oxidation at mild applied potentials of -255 mV vs ferrocene, which is the [Ru2(chp)4(NH3)]0/+ redox potential. We now report a comprehensive computational investigation of possible mechanisms for this reaction and electronic structure analysis of key intermediates therein. We extend this analysis to proposed second-generation electrocatalysts bearing structurally similar fhp and hmp (2-fluoro-6-hydroxypyridinate and 2-hydroxy-6-methylpyridinate, respectively) equatorial ligands, and we further expand this study from Ru2 to analogous Os2 cores. Predicted M24+/5+ redox potentials, which we expect to correlate with experimental AOR overpotential, depend strongly on the identity of the metal center, and to a lesser degree on the nature of the equatorial supporting ligand. Os2 complexes are easier to oxidize than analogous Ru2 complexes by ∼640 mV, on average. In contrast to mono-Ru catalysts, which oxidize ammonia via a rate-limiting activation of the strong N-H bond, we find lowest-energy reaction pathways for Ru2 and Os2 complexes that involve direct N-N bond formation onto electrophilic intermediates having terminal amido, imido, or nitrido groups. While transition state energies for Os2 complexes are high, those for Ru2 complexes are moderate and notably lower than those for mono-Ru complexes. We attribute these lower barriers to enhanced electrophilicity of the Ru2 intermediates, which is a consequence of their metal-metal bonded structure. Os2 intermediates are found to be, surprisingly, less electrophilic, and we suggest that Os2 complexes may require access to oxidation states higher than Os25+ in order to perform AOR at reasonable reaction rates.

Electronic Structure of Ru26+ Complexes with Electron-Rich Anilinopyridinate Ligands.

Diruthenium paddlewheel complexes supported by electron-rich anilinopyridinate (Xap) ligands were synthesized in the course of the first in-depth structural and spectroscopic interrogation of monocationic [Ru2(Xap)4Cl]+ species in the Ru26+ oxidation state. Despite paramagnetism of the compounds, 1H NMR spectroscopy proved highly informative for determining the isomerism of the Ru25+ and Ru26+ compounds. While most compounds are found to have the polar (4,0) geometry, with all four Xap ligands in the same orientation, some synthetic procedures resulted in a mixture of (4,0) and (3,1) isomers, most notably in the case of the parent compound Ru2(ap)4Cl. The isomerism of this compound has been overlooked in previous reports. Electrochemical studies demonstrate that oxidation potentials can be tuned by the installation of electron donating groups to the ligands, increasing accessibility of the Ru26+ oxidation state. The resulting Ru26+ monocations were found to have the expected (π*)2 ground state, and an in-depth study of the electronic transitions by Vis/NIR absorption and MCD spectroscopies with the aid of TD-DFT allowed for the assignment of the electronic spectra. The empty δ* orbital is the major acceptor orbital for the most prominent electronic transitions. Both Ru25+ and Ru26+ compounds were studied by Ru K-edge X-ray absorption spectroscopy; however, the rising edge energy is insensitive to redox changes in the compounds due to the broad line shape observed for 4d transition metal K-edges. DFT calculations indicate the presence of ligand orbitals at the frontier level, suggesting that further oxidation beyond Ru26+ will be ligand-centered rather than metal-centered.

Computational analysis of metal-metal bonded dimetal tetrabenzoate redox potentials in the context of ammonia oxidation electrocatalysis.

Metal-metal bonded complexes are promising candidates for catalyzing redox transformations. Of particular interest is the oxidation of ammonia to dinitrogen, an important half reaction for the potential utilization of ammonia as a fuel or hydrogen carrier. This work computationally explores 30 different metal-metal bonded dimers (5 different metal centers and 6 different benzoate ligand derivatives) to explore the tunability of the redox potential when ammonia is bound to the complexes as an axial ligand, modeling the first step in ammonia oxidation electrocatalysis. We calculate the redox potentials of these compounds, making reference to experimental data when appropriate, identifying two degrees of tunability: a coarse adjustment, changing the metal center, allows for a wide range of redox potentials to be accessed (from +1.0 to -2.0 V vs. ferrocene/ferrocenium in acetonitrile solution) and a fine adjustment, the para-substituent of the benzoate derivative, which affects the redox potential in a smaller range based on the electron donating/withdrawing effects of the substituent. Ruthenium and osmium tetrabenzoate catalysts are prime candidates for next generation ammonia oxidation catalysts because their redox potentials fall within the direct ammonia fuel cell "viability zone" bracketed by the thermodynamic potentials of oxygen reduction (ORR) and nitrogen reduction (NRR). Rhodium tetrabenzoate species fall above the ORR potential, suggesting ammonia oxidation promoted by Rh2 catalysts could instead be used to facilitate hydrogen production through coupling to hydrogen evolution at a cathode. The redox potentials of rhenium and iridium tetrabenzoate catalysts fall below the NRR potential suggesting that these compounds could be further investigated in the context of electrochemical ammonia synthesis. Each redox event studied involves electron transfer from the M-M δ* orbital regardless of choice of metal or benzoate ligand derivative; this leads us to believe that the chemical reactivity of the various studied compounds will be similar in the context of ammonia oxidation.

Divergent C-H Amidations and Imidations by Tuning Electrochemical Reaction Potentials.

Electrochemical C-H functionalizations are attractive transformations, as they are capable of avoiding the use of transition metals, pre-oxidized precursors, or suprastoichiometric amounts of terminal oxidants. Herein an electrochemically tunable method was developed that enabled the divergent formation of cyclic amines or imines by applying different reaction potentials. Detailed cyclic voltammetry analyses, coupled with chronopotentiometry experiments, were carried out to provide insight into the mechanism, while atom economy was assessed through a paired electrolysis. Selective C-H amidations and imidations were achieved to afford five- to seven-membered sulfonamide motifs that could be employed for late-stage modifications.

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.