Bond Dissociation Energies of Carbonyl Gold Complexes: a New Descriptor of Ligand Effects in Gold(i) Complexes?

Ligand electronic effects in gold(i) chemistry have been evaluated by means of the experimental determination of M-CO bond dissociation energies for 16 [L-Au-CO] complexes, bearing L ligands widely used in gold catalysis. Energy-resolved analyses have been made using tandem mass spectrometry with collision-induced dissociation. Coupled with DFT calculations, this approach enables the quantification of ligand effects based on the LAu-CO bond strength. A further energy decomposition analysis gives access to detailed insights into this bond's characteristics. Whereas small differences are observed between phosphine- and phosphite-containing gold complexes, carbene ligands are shown to stabilize the gold-carbonyl bond much more efficiently.