Gold(iii)–arene complexes by insertion of olefins into gold–aryl bonds† †Electronic supplementary information (ESI) available: Experimental details (syntheses, analytical data and copies of 1H, 13C and 31P NMR spectra), crystallographic data of 2 and computational details. CCDC 1526613 and 1538015. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00145b Click here for additional data file. Click here for additional data file

The synthesis and characterization of the first gold( iii )–arene complexes are described. The synthesis and characterization of the first gold( iii )–arene complexes are described. Well-defined (P,C)-cyclometalated gold( iii )–aryl complexes were prepared and characterized by NMR spectroscopy. These complexes swiftly and cleanly reacted with norbornene and ethylene to provide cationic gold( iii )–alkyl complexes, in which the remote phenyl ring was η 2 -coordinated to gold. The interaction between the aromatic ring and the gold( iii ) center was thoroughly analyzed by NMR spectroscopy, X-ray diffraction, and DFT calculations. The π–arene coordination was found to significantly influence the stability and reactivity of low coordinated gold( iii ) alkyl species.