Catalytic applications of [IPr center dot GaX2][SbF6] and related species

The title cationic gallium(III) complexes are shown to be useful in homogeneous molecular catalysis. They have been used in catalytic reactions involving the activation of alcohols, alkynes and alkenes towards the addition of various nucleophiles (H2O, ROH, carbonyls, arenes, hydrides, etc.). The mechanism of the transformations of alkynes and alkenes are believed to involve carbocationic sigma-vinyl and sigma-alkyl gallium intermediates, which can be prone to unusual rearrangements and condensations. These species are likely to be formed reversibly, which confers a dynamic behavior to this chemistry. DFT computations shed light on these issues.