Gold Chemistry Guided by the Isolobality Concept†

Abstract

The general isolobality concept presented by Hoffmann, Stone, and Mingos in the early 1980s has had—tacitly or explicitly—a great impact on the development of many areas of inorganic, organometallic, and coordination chemistry. Pertinent considerations were fruitful especially in gold chemistry, because isolobal relations between gold(I) cations [Au]+ and their complexes [LAu]+ on the one hand and protons [H]+, various carbocations [R]+, and other simple species on the other are particularly obvious. Work guided by these relationships has included almost all fields of gold chemistry, from simple high-energy species in the gas phase to homoatomic clusters of gold atoms or heteroatomic aggregates with main-group and transition elements. Recent work has also concentrated on the specific mechanisms of reactions catalyzed either by protons or by the above gold cations with a variety of new ligands L in separate or tandem reaction sequences. The present review summarizes classical and current lines of research that have followed the original concept up to its present frontier version of “autogenic isolobality”.