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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… Click to show full abstract
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.
Journal Title: Journal of the American Chemical Society
Year Published: 2017
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