Electrooxidative Activation of B−B Bond in B₂cat₂: Access to <i>gem</i>‐Diborylalkanes via Paired Electrolysis

Abstract This report describes the unprecedented electrooxidation of a solvent (e.g., DMF)‐ligated B 2 cat complex, whereby solvent‐stabilized boryl radical is formed via quasi‐homolytic cleavage B−B bond in DMF‐ligated cation. Cyclic voltammetry and density functional theory provide evidence to support this novel activation strategy. Furthermore, strategy for electrochemical gem ‐diborylation ‐bromides paired electrolysis developed first time, affording range versatile ‐diborylalkanes, which are widely used synthetic society. Notably, reaction approach scalable, transition‐metal‐free, requires no external activator.