Dinuclear Gold Complexes Supported by Wide Bite Angle Diphosphines for Preorganization-Induced Selective Dual-Gold Catalysis
Marianne Lankelma,
Vincent Vreeken,
Maxime A. Siegler,
Jarl Ivar van der Vlugt
Affiliations
Marianne Lankelma
Homogeneous, Supramolecular, and Bio-inspired Catalysis, van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
Vincent Vreeken
Homogeneous, Supramolecular, and Bio-inspired Catalysis, van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
Maxime A. Siegler
Small Molecule X-ray Laboratory, Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA
Jarl Ivar van der Vlugt
Homogeneous, Supramolecular, and Bio-inspired Catalysis, van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
The synthesis, reactivity, and potential of well-defined dinuclear gold complexes as precursors for dual-gold catalysis is explored. Using the preorganizing abilities of well-known wide bite angle diphosphine ligands, DBFPhos and DPEPhos, dinuclear Au(I)⁻Au(I) complexes 1 and 2 are used as precursors to form well-defined monocationic species with either a chlorido- or acetylido-ligand bridging the two gold centers. These compounds are active catalysts for the dual-gold heterocycloaddition of a urea-functionalized alkyne, and the preorganization of both Au-centers affords efficient σ,π-activation of the substrate, even at high dilution, significantly outperforming benchmark mononuclear catalysts.
