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

Matthieu Regnacq (1) , Denis Lesage (1) , Marte Holmsen (2) , Karinne Miqueu (3) , Didier Bourissou (4) , Yves Gimbert (5)

1 IPCM - Institut Parisien de Chimie Moléculaire
2 UiO - University of Oslo
3 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
4 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
5 DCM - Département de Chimie Moléculaire

(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.

Domaines: Matériaux; Chimie analytique; Polymères; Chimie théorique et/ou physique

Matthieu Regnacq, Denis Lesage, Marte Holmsen, Karinne Miqueu, Didier Bourissou, et al.. Energetics of key Au( iii )-substrate adducts relevant to catalytic hydroarylation of alkynes. Dalton Transactions, 2023, 52 (38), pp.13528-13536. ⟨10.1039/d3dt02393a⟩. ⟨hal-04243590⟩