Cationic gold(III) alkyl complexes: generation, trapping, and insertion of norbornene

Angew Chem Int Ed Engl. 2015 Jan 19;54(4):1266-9. doi: 10.1002/anie.201409604. Epub 2014 Oct 29.

Abstract

Migratory insertion of alkenes into gold-carbon bonds, a fundamental yet unprecedented organometallic transformation, has been investigated from a discrete (P,C) cyclometalated gold(III) dimethyl complex. Methide abstraction by B(C6F5)3 is shown to generate a highly reactive cationic Au(III) complex that evolves spontaneously by C6F5 transfer from boron. In the presence of norbornene, migratory insertion into the Au-C bond proceeds readily. The resulting norbornyl complex is efficiently trapped with pyridines or chloride to give stable four-coordinate adducts.

Keywords: Lewis acids; gold; insertion reactions; olefins; organometallic chemistry.