We have conducted a theoretical exploration of the ligand electronic effect in the protodeauration step of a model gold(I) cyclization reaction, for which experimental data are available. The mechanism of the protodeauration is investigated through a density functional theory (DFT) approach, and the electron-donating power of the ligand is quantified through the charge displacement function (CDF). We find that the frequently encountered assumption in the literature that "strong electron-donating ligands accelerate the protodeauration" can be set into a quantitative framework by our combined DFT/CDF theoretical approach, which allows us also to rationalize the highest catalytic efficiency of Buchwald phosphine type ligands in this process. We analyze the ligand effect on the gold complex-substrate (LAu-S) bond strength, namely the bond to be broken during the protodeauration, and we find that the LAu-S interaction energies linearly correlate with the activation barriers. Finally, energy decomposition analysis (EDA) is used to investigate the LAu-S bond, and we show that changes in the interaction energies are mainly due to changes in the electrostatic component, whose value is in turn modulated by the ligand electron-donating power.
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© 2016 American Chemical Society.