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  1. Abstract

    High‐valent metal‐oxo species play critical roles in enzymatic catalysis yet their properties are still poorly understood. In this work we report a combined experimental and computational study into biomimetic iron(IV)‐oxo and iron(III)‐oxo complexes with tight second‐coordination sphere environments that restrict substrate access. The work shows that the second‐coordination sphere slows the hydrogen atom abstraction step from toluene dramatically and the kinetics is zeroth order in substrate. However, the iron(II)‐hydroxo that is formed has a low reduction potential and hence cannot do OH rebound favorably. The tolyl radical in solution then reacts further with alternative reaction partners. By contrast, the iron(IV)‐oxo species reacts predominantly through OH rebound to form alcohol products. Our studies show that the oxidation state of the metal influences reactivities and selectivities with substrate dramatically and that enzymes will likely need an iron(IV) center to catalyze C−H hydroxylation reactions.

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    Free, publicly-accessible full text available July 26, 2024
  2. Free, publicly-accessible full text available August 17, 2024
  3. Free, publicly-accessible full text available May 1, 2024
  4. 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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  5. The cobalt pyridinophane complex [Co( H N4)Cl 2 ] + ( H N4 = 3,7-diaza-1,5(2,6)-dipyridinacyclooctaphane) is converted under catalytic conditions to an electrode-adsorbed species. Aqueous Co 2+ solutions similarly deposit a species under these conditions. Surface characterization reveals the formation of Co nanoparticles. These nanoparticles are active in the electrocatalytic redution of aqueous nitrate. 
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  6. Over the past century, the global concentration of environmental nitrate has increased significantly from human activity, which has resulted in the contamination of drinking water and aquatic hypoxia around the world, so the development of effective nitrate-reducing agents is urgent. This work compares three potential macrocycle-based nitrate reduction electrocatalysts: [Co(DIM)] 3+ , [Co(cyclam)] 3+ and [Co(TIM)] 3+ . Although all three complexes have similar structures, only [Co(DIM)] 3+ has been experimentally determined to be an active electrocatalyst for selective nitrate reduction to produce ammonia in water. While [Co(cyclam)] 3+ can reduce aqueous nitrate to ammonia and hydroxylamine at heavy metal electrodes, [Co(TIM)] 3+ is inactive for the reduction of nitrate. As an initial step to understanding what structural and electronic properties are important for efficient electrocatalysts for nitrate reduction, density functional theory (DFT) was employed to investigate the electronic structure of the three Co complexes, with the reduction potentials calibrated to experimental results. Moreover, DFT was employed to explore four different reaction mechanisms for the first steps of nitrate reduction. The calculated reaction barriers reveal how a combination of electron transfer in a redox non-innocent complex, substrate binding, and intramolecular hydrogen bonding dictates the activity of Co-based catalysts toward nitrate reduction. 
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