Nickel-catalyzed oxidative fluoroalkylation of aryl halides via paired electrolysis

The paired electrolysis triggers multiple oxidative and reductive processes to occur simultaneously, which ensures the steady transformation of the intermediates to the desired coupling products. However, fluoroalkyl radicals have not been harnessed for metal-catalyzed cross-coupling with aryl halides under electrochemical conditions. This work describes a general strategy for rapid access to various fluoromethyl and difluoromethyl aromatics by paired electrolysis. The contradiction between anodic oxidation of fluoroalkyl sulfinates and cathodic reduction of low-valent nickel catalysts can be well addressed under mild cell conditions, allowing for direct introduction of fluorinated functionalities into aromatic systems.

Electrolytic Reduction of Titanium Dioxide in Molten LiCl–Li2O

The electrolytic reduction of TiO2 in LiCl–Li2O (1 wt.%) at 650 °C was investigated under a series of cathodic reduction potentials and applied charges to provide a mechanistic understanding of the electrochemical characteristics of the system. The optimal cathodic reduction potential was determined as being −0.3 V vs. Li/Li+. Li2TiO3 and LiTiO2 were structurally identified as intermediate and partial reduction products of the TiO2 electrolytic reduction. The reduction of LiTiO2 was extremely slow and reversible due to its high stability and the detrimental effect of Li2O accumulation within the solid particles. The most reduced product obtained in this study was LiTiO2, which was achieved when using 150% of the theoretical charge under the optimal reduction potential. The highest reduction extent obtained in this study was 25%. Based on theoretical DFT modeling, a detailed multistep reduction mechanism and scheme were proposed for TiO2 electrolytic reduction in LiCl–Li2O (1 wt.%) at 650 °C.