ABSTRACT
Management of the electrode surface temperature is an understudied aspect of (photo)electrode reactor design for complex reactions, such as CO2 reduction. In this work, we study the impact of local electrode heating on electrochemical reduction of CO2 reduction. Using the ferri/ferrocyanide open circuit voltage as a reporter of the effective reaction temperature, we reveal how the interplay of surface heating and convective cooling presents an opportunity for cooptimizing mass transport and thermal assistance of electrochemical reactions, where we focus on reduction of CO2 to carbon-coupled (C2+) products. The introduction of an organic coating on the electrode surface facilitates well-behaved electrode kinetics with near-ambient bulk electrolyte temperature. This approach helps to probe the fundamentals of thermal effects in electrochemical reactions, as demonstrated through Bayesian inference of Tafel kinetic parameters from a suite of high throughput experiments, which reveal a decrease in overpotential for C2+ products by 0.1 V on polycrystalline copper via 60 °C surface heating.
ABSTRACT
Two epoxidation catalysts, one of which consists of two VANOL ligands and an aluminum and the other that consists of two VANOL ligands and a boron, were compared. Both catalysts are highly effective in the catalytic asymmetric epoxidation of a variety of aromatic and aliphatic aldehydes with diazoacetamides, giving high yields and excellent asymmetric inductions. The aluminum catalyst is effective at 0 °C and the boron catalyst at -40 °C. Although both the aluminum and boron catalysts of (R)-VANOL give very high asymmetric inductions (up to 99% ee), they give opposite enantiomers of the epoxide. The mechanism, rate- and enantioselectivity-determining step, and origin of enantiodivergence are evaluated using density functional theory calculations.
ABSTRACT
Photochemical radical generation has become a modern staple in chemical synthesis and methodology. Herein, we detail the photochemistry of a highly reducing, highly luminescent dicopper system [Cu2] (Eox* ≈ -2.7 V vs SCE; τ0 ≈ 10 µs) within the context of a model reaction: single-electron reduction of benzyl chlorides. The dicopper system is mechanistically well defined. As we show, it is the [Cu2]* excited state that serves as the outer-sphere photoreductant of benzyl chloride substrates; the ground-state oxidized byproduct, [Cu2]+, is electrochemically recycled, demonstrating a catalytic electrophotochemical C-C coupling process.
ABSTRACT
Boroxinate complexes of VAPOL and VANOL are a chiral anionic platform that can serve as a versatile staging arena for asymmetric catalysis. The structural underpinning of the platform is a chiral polyborate core that covalently links together alcohols (or phenols) and vaulted biaryl ligands. The polyborate platform is assembled in situ by the substrate of the reaction, and thus a multiplex of chiral catalysts can be rapidly assembled from various alcohols (or phenols) and bis-phenol ligands for screening of catalyst activity. In the present study, variations in the steric and electronic properties of the phenol/alcohol component of the boroxinate catalyst are probed to reveal their effects on the asymmetric induction in the catalytic asymmetric aziridination reaction. A Hammett study is consistent with a mechanism in which the two substrates are hydrogen-bonded to the boroxinate core in the enantiogenic step. The results of the Hammett study are supported by a computational study in which it is found that the H-O distance of the protonated imine hydrogen bonded to the anionic boroxinate core decreases with an increase in the electron releasing ability of the phenol unit incorporated into the boroxinate. The results are not consistent with a mechanism in which the boroxinate catalyst functions as a Lewis acid and activates the imine by a Lewis acid/Lewis base interaction.
