Reductive Eliminations from λ³-Iodanes: Understanding Selectivity and the Crucial Role of the Hypervalent Bond

This computational study investigates the factors governing the selectivity of the reductive eliminations from rapidly equilibrating isomeric λ³-iodanes derived from a diaryl iodonium salt and a nucleophile. The chemoselectivity is mainly determined by the partial charge at the ipso-carbon atom involved in the 3-center–4-electron bond.