Direct Formation of Carbon(sp)-Heteroatom Bonds from Rh To Produce Methyl Iodide, Thioethers, and Alkylamines.

Thermolysis of the Rh-Me complex (DPEphos)RhMeI (1) results in reductive elimination of MeI. Mechanistic studies are consistent with S2 attack by I at the Rh-Me group via two separate competing paths. Addition of sulfur and nitrogen nucleophiles allows effective competition and formation of C(sp)-S and C(sp)-N coupled products in high yields. C(sp)-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.