Partially oxidized gold nanoparticles: a catalytic base-free system for the aerobic homocoupling of alkynes

The mechanism of alkyne homocoupling over gold nanoparticles and clusters, isolated and supported on CeO2, has been theoretically investigated by means of periodic DFT calculations. The theoretical study indicates that O2 dissociation on gold generates basic O atoms able to abstract the proton of the alkyne, and cationic Aud+ and Au+ species that decrease the activation barrier for the CAC bond forming step. Kinetic results show that the base-free homocoupling of alkynes is effectively catalyzed by gold nanoparticles supported on different solids, and confirm the theoretical predictionFinancial support from Spanish MCIINN (Consolider Ingenio 2010-MULTICAT CSD2009-00050 and Subprograma de apoyo a Centros y Universidades de Excelencia Severo Ochoa SEV 2012 0267 Projects) is acknowledged. Red Espanola de Supercomputacion (RES) and Centre de Calcul de la Universitat de Valencia are gratefully acknowledged for computational facilities and technical assistance. A.L.-P. and J.O.-M. also thank ITQ for a contract.Boronat Zaragoza, M.; Laursen, SO.; Leyva Perez, A.; Oliver Meseguer, J.; Cómbita Merchán, DF.; Corma Canós, A. (2014). Partially oxidized gold nanoparticles: a catalytic base-free system for the aerobic homocoupling of alkynes. Journal of Catalysis. 315:6-14. https://doi.org/10.1016/j.jcat.2014.04.00361431