Direct Formation of Carbon(sp 3 )-Heteroatom Bonds from Rh III 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 SN 2 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.