Direct Formation of Carbon(sp3)–Heteroatom Bonds from RhIII To Produce Methyl Iodide, Thioethers, and Alkylamines

Thermolysis of the RhIII–Me complex (DPEphos)­RhMeI2 (1) results in reductive elimination of MeI. Mechanistic studies are consistent with SN2 attack by I− at the RhIII–Me group via two separate competing paths. Addition of sulfur and nitrogen nucleophiles allows effective competition and formation of C­(sp3)–S and C­(sp3)–N coupled products in high yields. C­(sp3)–N bond formation is second-order in amine, consistent with amine substitution of iodide at the metal followed by nucleophilic attack at carbon by a second amine.