Harnessing non-covalent interactions synthesis & catalysis

Placing gold on a π+-surface: ligand design and impact on reactivity Wei-Chun Liu and François Gabbaï Texas A&M University, USA As part of our continuing interest in modulating the reactivity of late-transition metal complexes, we have developed a series of gold chloride complexes supported by ambiphilic phosphine ligands featuring a xanthylium cation as the electron poor unit. In this presentation, I will describe a novel type of gold chloride complex in which AuCl moiety interacts with π+ surface of the xanthylium cations 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. The presentation will end by a comparison of the catalytic reactivity of the xanthylium complex with its significantly less active acridinium and the 9-oxa- 10-boraanthracene analogues. References 1. Chem. Sci. , 2023 , 14 , 277-283 2. Chem. Commun. 2021 , 57 , 10154-10157. 3. Chem. Sci. 2021 , 12 , 3929-3936. 4. Angew . Chem. Int. Ed. 2019 , 58 , 18266-18270.

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