Uncovering the Importance of Proton Donors in TmI2‐Promoted Electron Transfer: Facile CN Bond Cleavage in Unactivated Amides

Nonclassical lanthanide(II) iodides are modern reagents for the development of challenging electron-transfer processes. It was demonstrated that alcohols are critical for the formation of a thermodynamically more powerful reductant from TmI2 (thulium diiodide), the first nonclassical lanthanide(II) iodide in the series (TmI2, DyI2, NdI2). The TmI2(ROH)n reagent promotes an unprecedented cleavage of the σ CN bond in amides.