Placing gold on a π+-surface: ligand design and impact on reactivity

Abstract

We describe a novel gold chloride complex supported by an ambiphilic phosphine/xanthylium ligand in which the AuCl moiety interacts with the π⁺ surface of the xanthylium unit as indicated by structural studies. Energy decomposition analyses carried out on a model system indicates the prevalence of non-covalent interactions in which the electrostatic and dispersion terms cumulatively dominate. The presence of these AuCl–π⁺ interactions correlates with the high catalytic activity of this complex in the cyclisation of 2-(phenylethynyl)phenylboronic acid, N-propargyl-t-butylamide, and 2-allyl-2-(2-propynyl)malonate. Comparison with the significantly less active acridinium and the 9-oxa-10-boraanthracene analogues reinforces this conclusion.