Theoretical study of the electron-donating effects of thiourea ligands in catalysis

Thiourea and its derivatives often act as strong electron-donating ligands in palladium-catalyzed reactions. Density functional theory calculations were performed to investigate the electronic effects of thiourea ligands in palladium complexes, and a p-d-pi interaction model is proposed. In this model, a Pd(d)-S(p) interaction is responsible for the increased binding of IC acceptor ligands such as CO and olefins, which are present in important intermediates in Pd-catalyzed reactions. This d-p interaction is a four-electron, two-orbital interaction; it raises the energy of the Pd(d(yz)) orbital, bringing it closer to the pi* orbital of the CO or olefin ligand, and increases back donation. Thiourea-ligated transition metals are therefore favorable for the binding of acidic pi ligands. (c) 2014 Elsevier B.V. All rights reserved.Chemistry, PhysicalSCI(E)EI0ARTICLEZyang@pku.edu.cn; Lanyu@cqu.edu.cn527-533107