The Pincer Ligand Supported Ruthenium Catalysts for Acetylene Hydrochlorination: Molecular Mechanisms from Theoretical Insights

Abstract

Pincer ligand supported RuII chloride complexes may be used for acetylene hydrochlorination as non-mercury molecular catalysts. Based on theoretical calculations, the catalytic mechanism and the interaction between catalysts and reactants has been evaluated, indicating that the (pincer)RuIICl2 platform supports electrophilic proton-ruthenation of C2H2. Energy decomposition studies further illustrate the electron-rich property of the RuII center, which can increase the negative charge of C2H2 via 4d-electron backdonation. Thus, the electrophilic reaction mechanism is favored due to lower energetic barriers. By improving the electron-donating ability of ligands, this lowering of energetic barriers can be enhanced. Therefore, non-mercury catalysts for acetylene hydrochlorination with milder reaction conditions and higher catalytic activity can be designed.

Keywords

• acetylene hydrochlorination
• reaction mechanism
• ruthenium complex molecular catalyst
• DFT calculations