Photochemical Reduction of Quinolines with γ-Terpinene.

The saturation of aromatic scaffolds is valuable for the synthesis of complex rings. Herein, we demonstrate a process for photochemical dearomative reduction of quinolines. The process involves capture of a quinoline excited state with γ-terpinene. Importantly, the reaction is chemoselective as other easily reduced functionalities such as halogens or alkenes do not undergo reduction. The mechanism of the reaction has also been investigated. Finally, the generality of the approach towards other substrates is demonstrated.

A Spectroscopically Observed Iron Nitrosyl Intermediate in the Reduction of Nitrate by a Surface-Conjugated Electrocatalyst.

We report an iron-based graphite-conjugated electrocatalyst (GCC-FeDIM) that combines the well-defined nature of homogeneous molecular electrocatalysts with the robustness of a heterogeneous electrode. A suite of spectroscopic methods, supported by the results of DFT calculations, reveals that the electrode surface is functionalized by high spin (S = 5/2) Fe(III) ions in an FeN4Cl2 coordination environment. The chloride ions are hydrolyzed in aqueous solution, with the resulting cyclic voltammogram revealing a Gaussian-shaped wave assigned to 1H+/1e- reduction of surface Fe(III)-OH surface. A catalytic wave is observed in the presence of NO3-, with an onset potential of -1.1 V vs SCE. At pH 6.0, GCC-FeDIM rapidly reduces NO3- to ammonium and nitrite with 88 and 6% Faradaic efficiency, respectively. Mechanistic studies, including in situ X-ray absorption spectroscopy, suggest that electrocatalytic NO3- reduction involves an iron nitrosyl intermediate. The Fe-N bond length (1.65 Å) is similar to that observed in {Fe(NO)}6 complexes, which is supported by the results of DFT calculations.

Buffer Assists Electrocatalytic Nitrite Reduction by a Cobalt Macrocycle Complex.

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.

Strain-Release [2π + 2σ] Cycloadditions for the Synthesis of Bicyclo[2.1.1]hexanes Initiated by Energy Transfer.

Saturated bicycles are becoming ever more important in the design and development of new pharmaceuticals. Here a new strategy for the synthesis of bicyclo[2.1.1]hexanes is described. These bicycles are significant because they have defined exit vectors, yet many substitution patterns are underexplored as building blocks. The process involves sensitization of a bicyclo[1.1.0]butane followed by cycloaddition with an alkene. The scope and mechanistic details of the method are discussed.

Photosensitized [2+2]-Cycloadditions of Alkenylboronates and Alkenes.

A new strategy for the synthesis of highly versatile cyclobutylboronates via the photosensitized [2+2]-cycloaddition of alkenylboronates and alkenes is presented. The process is mechanistically different from other processes in that energy transfer occurs with the alkenylboronate as opposed to the other alkene. This strategy allows for the synthesis of an array of diverse cyclobutylboronates. The conversion of these adducts to other compounds as well as their utility in the synthesis of melicodenine C is demonstrated.

Electrocatalytic nitrate reduction with Co-based catalysts: comparison of DIM, TIM and cyclam ligands.

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.

Graphite Conjugation of a Macrocyclic Cobalt Complex Enhances Nitrite Electroreduction to Ammonia.

This work reports on the generation of a graphite-conjugated diimine macrocyclic Co catalyst (GCC-CoDIM) that is assembled at o-quinone edge defects on graphitic carbon electrodes. X-ray photoelectron spectroscopy and X-ray absorption spectroscopy confirm the existence of a new Co surface species with a coordination environment that is the same as that of the molecular analogue, [Co(DIM)Br2]+. GCC-CoDIM selectively reduces nitrite to ammonium with quantitative Faradaic efficiency and at a rate that approaches enzymatic catalysis. Preliminary mechanistic investigations suggest that the increased rate is accompanied by a change in mechanism from the molecular analogue. These results provide a template for creating macrocycle-based electrocatalysts based on first-row transition metals conjugated to an extreme redox-active ligand.

Correction: Electrode-adsorption activates trans-[Cr(cyclam)Cl2]+ for electrocatalytic nitrate reduction.

Correction for 'Electrode-adsorption activates trans-[Cr(cyclam)Cl2]+ for electrocatalytic nitrate reduction' by Sarah E. Braley et al., Chem. Commun., 2020, 56, 603-606, DOI: 10.1039/C9CC08550E.

Electrode-adsorption activates trans-[Cr(cyclam)Cl2]+ for electrocatalytic nitrate reduction.

Cyclic voltammetry reveals that aqueous trans-[Cr(cyclam)Cl2]+ is reversibly reduced at a mercury electrode, with a small prewave suggesting an adsorptive interaction between the complex and electrode surface. A catalytic current is observed in the presence of excess nitrate, with the onset potential for catalysis at the prewave. Nitrate is electrocatalytically reduced to nitrite, with preliminary mechanistic investigations implicating a chromium oxo intermediate.