CHAPTER 26. Role of Ion Pairing in the Mechanisms of Au(i)-catalysed Reactions: Theory and Experiment

In this chapter, the role of ion pairing in the mechanism of the reactions promoted by gold(i) catalysts L–Au–X is elucidated by means of both experimental findings and theoretical calculations. The synergy of the approach allowed the full elucidation of the role of the counterion X−. The catalytic performance in the alkoxylation and hydration of alkynes promoted by gold(i) is influenced by the coordinating ability and basicity (proton affinity) of the counterion, the anion/cation relative orientation and the appropriate matching of X− and L. Finally, how the nature of the anion plays a fundamental role in solvent-, silver- and acid-free gold(i)-catalysed hydration of alkynes is highlighted.