Energetics of key Au()-substrate adducts relevant to catalytic hydroarylation of alkynes

(P,C)-cyclometalated Au( iii ) complexes have shown remarkable ability to catalyze the intermolecular hydroarylation of alkynes. Evidence of an outer-sphere mechanism has been provided in a previous study and is confirmed here by analysing the experimental data and DFT calculations. In this work, we propose evaluation of critical energies of dissociation of Au( iii ) complexes with different substrates via energy-resolved mass spectrometry (ERMS) experiments and kinetic modelling. The kinetic model is based on a multi-collisional approach. On the one hand, the classification confirms the mechanism previously proposed; on the other hand, it supports the collisional model and its application to particularly fragile adducts. (P,C)-cyclometalated Au( iii ) complexes have shown remarkable ability to catalyze the intermolecular hydroarylation of alkynes.