Gold Chemistry Guided by the Isolobality Concept

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.