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  1. This work reports a combined experimental and computational study of the activation of an otherwise catalytically inactive cobalt complex, [Co(TIM)Br2]+, for aqueous nitrite reduction. The presence of phosphate buffer leads to efficient electrocatalysis, with rapid reduction to ammonium occurring close to the thermodynamic potential and with high Faradaic efficiency. At neutral pH, increasing buffer concentrations increase catalytic current while simultaneously decreasing overpotential, although high concentrations have an inhibitory effect. Controlled potential electrolysis and rotating ring-disk electrode experiments indicate that ammonium is directly produced from nitrite by [Co(TIM)Br2]+, along with hydroxylamine. Mechanistic investigations implicate a vital role for the phosphate buffer, specifically as a proton shuttle, although high buffer concentrations inhibit catalysis. These results indicate a role for buffer in the design of electrocatalysts for nitrogen oxide conversion. 
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  2. High-valent iron species are key intermediates in oxidative biological processes, but hexavalent complexes apart from the ferrate ion are exceedingly rare. Here, we report the synthesis and structural and spectroscopic characterization of a stable Fe(VI) complex (3) prepared by facile one-electron oxidation of an Fe(V) bis(imido) (2). Single-crystal x-ray diffraction of2and3revealed four-coordinate Fe centers with an unusual “seesaw” geometry.57Fe Mössbauer, x-ray photoelectron, x-ray absorption, and electron-nuclear double resonance (ENDOR) spectroscopies, supported by electronic structure calculations, support a low-spin (S= 1/2) d3Fe(V) configuration in2and a diamagnetic (S= 0) d2Fe(VI) configuration in3. Their shared seesaw geometry is electronically dictated by a balance of Fe-imido σ- and π-bonding interactions.

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  5. Mechanistic investigations into electrocatalytic nitrate reduction by a cobalt complex reveal the critical role played by the flexible, redox-active ligand.

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