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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. [ABSTRACT FROM AUTHOR]

Thanks to their unique electronic and steric properties, carbene ligands offer highly valuable features for catalysis, including homogenous gold catalysis. The use of carbene-gold complexes has improved existing reactions, either by modifying reactivity modes or by leading to highly asymmetric processes. These topics will be discussed on the basis of selected examples. [ABSTRACT FROM AUTHOR]

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