A Systematic Study of the Effects of Complex Structure on Aryl Iodide Oxidative Addition at Bipyridyl‐Ligated Gold(I) Centers

Abstract

Acombined theoretical and experimental approach has been used to study the unusual mechanism of oxidative addition of aryl iodides to [bipyAu(C 2 H 4 )] + complexes.T he modular nature of this system allowed asystematic assessment of the effects of complex structure.C omputational comparisons between cationic gold and the isolobal (neutral) Pd 0 and Pt 0 complexes revealed similar mechanistic features,b ut with oxidative addition being significantly favored for the group 10 metals.F urther differences between Au and Pd were seen in experimental studies:s tudying reaction rates as af unction of electronic and steric properties showed that ligands bearing more electron-poor functionality increase the rate of oxidative addition;i nacomplementary way, electron-rich aryl iodides give faster rates.T his divergence in mechanism compared to Pd suggests that Ar À Xo xidative addition with Au can underpin ab road range of new or complementary transformations.Scheme 1. Oxidative addition at transition metal centers.