Mechanistic details for oxidative addition of PhICl 2 to gold(I) complexes.

This study demonstrates that the oxidative addition of hypervalent iodine PhICl 2 to Au(I) complexes LAuAr follows an unprecedented stepwise mechanism. The energy of the Au(I) d x 2 - y 2 orbital determines the ease of the oxidative addition reaction; the fewer electron-withdrawing substituents present on the Ar ligand, the higher the energy of the d x 2 -y 2 orbital and the easier the oxidative addition.