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2,2’-Bis(4-dimethylaminophenyl)- and 2,2'-dicyclohexyl-1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d]imidazole ((N-DMBI)2 and (Cyc-DMBI)2) are quite strong reductants with effective potentials of ca. −2 V vs ferrocenium/ferrocene, yet are relatively stable to air due to the coupling of redox and bond-breaking processes. Here, we examine their use in accomplishing electron transfer-induced bond-cleavage reactions, specifically dehalogenations. The dimers reduce halides that have reduction potentials less cathodic than ca. −2 V vs ferrocenium/ferrocene, especially under UV photoexcitation (using a 365 nm LED). In the case of benzyl halides, the products are bibenzyl derivatives, whereas aryl halides are reduced to the corresponding arenes. The potentials of the halides that can be reduced in this way, quantum-chemical calculations, and steady-state and transient absorption spectroscopy suggest that UV irradiation accelerates the reactions via cleavage of the dimers to the corresponding radical monomers.

Summary: This work maps the thermodynamics of electrochemically generated C-nucleophiles for reactive capture of CO2. We identify a linear relationship between the pKa, the reduction potential of a protonated nucleophile (Ered), and the nucleophile’s free energy of CO2 binding (ΔGbind). Through synergistic experiments and computations, this study establishes a three-parameter correlation described by the equation ΔGbind=−0.78pKa+4.28Ered+20.95 for a series of twelve imidazol(in)ium/N-heterocyclic carbene pairs with an R2 of 0.92. The correlation allows us to predict the ΔGbind of C-nucleophiles to CO2 using reduction potentials or pKas of imidazol(in)ium cations. The carbenes in this study were found to exhibit a wide range CO2 binding strengths, from strongly CO2 binding to nonspontaneous. This observation suggests that the ΔGbind of imidazol(in)ium-based carbenes is tunable to a desired strength by appropriate structural changes. This work sets the stage for systematic energetic tuning of electrochemically enabled reactive separations.

The decrease of total amount of atmospheric CO2 is an important societal challenge in which CO2 reduction has an important role to play. Electrocatalytic CO2 reduction with homogeneous catalysts is based on highly tunable catalyst design and exploits an abundant C1 source to make valuable products such as fuels and fuel precursors. These methods can also take advantage of renewable electricity as a green reductant. Mn-based catalysts offer these benefits while incorporating a relatively cheap and abundant first-row transition metal. Historically, interest in this field started with Mn(bpy-R)(CO)3X, whose performance matched that of its Re counterparts while achieving substantially lower overpotentials. This review examines an emerging class of homogeneous Mn-based electrocatalysts for CO2 reduction, Mn complexes with meridional tridentate coordination also known as Mn pincers, most of which contain redox-active ligands that enable multi-electron catalysis. Although there are relatively few examples in the literature thus far, these catalysts bring forth new catalytic mechanisms not observed for the well-established Mn(bpy-R)(CO)3X catalysts, and show promising reactivity for future studies.

This work describes new methods for the chemical recycling of end-use poly(ethylene terephthalate) (PET) in batch, microwave and electrochemical reactors. The reactions are based on basic hydrolysis of the ester moieties in the polymer framework and occur under mild reaction conditions with low-cost reagents. We report end-use PET depolymerization in refluxing methanol with added NaOH with 75% yield of terephthalic acid in batch after 12 h, while yields up to 65% can be observed after only 40 min under microwave irradiation at 85 °C. Using basic conditions produced in the electrochemical reduction of protic solvents, electrolytic experiments have been shown to produce 17% terephthalic acid after 1 h of electrolysis at −2.2 V vs. Ag/AgCl in 50% water/methanol mixtures with NaCl as a supporting electrolyte. The latter method avoids the use of caustic solutions containing high-concentration NaOH at the outset, thus proving the concept for a novel, environmentally benign method for the electrochemical recycling of end-use PET based on low-cost solvents (water and methanol) and reagents (NaCl and electricity).