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The development of reductive electrosynthetic reactions is often enabled by the oxidation of a sacrificial metal anode, which charge-balances the reductive reaction of interest occurring at the cathode. The metal...

Addition of halide salts as co-supporting electrolytes is a simple electrolyte tailoring strategy for enabling Al sacrificial anodes in THF-based electrolytes.

Samarium diiodide (SmI₂) is widely used as a strong one‐electron reducing agent and is often employed to form C−C bonds in complex systems. Despite their utility, SmI₂and related salts suffer from several drawbacks that render the use of Sm reducing agents in large‐scale synthesis impractical. Here, we report factors influencing the electrochemical reduction of Sm(III) to Sm(II), towards the goal of electrocatalytic Sm(III) reduction. We probe the effect of supporting electrolyte, electrode material, and Sm precursor on Sm(II)/(III) redox and on the reducing power of the Sm species. We find that the coordination strength of the counteranion of the Sm salt affects the reversibility and redox potential of the Sm(II)/(III) couple and establish that the counteranion primarily determines the reducibility of Sm(III). Electrochemically generated SmI₂performs similarly to commercial SmI₂solutions in a proof‐of‐concept reaction. The results will provide fundamental insight to facilitate the development of Sm‐electrocatalytic reactions.