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.