Efficient dimerization of perfluoroolefin with strong nucleophilic ionic liquid catalysts by adjusting the interaction of anions and cations

According to the requirements of sustainable green development, the efficient green synthesis of fluorine chemical products is an inevitable trend. In this work, we used ionic liquids as an effective catalyst in an important fluorochemical reaction – hexafluoropropylene dimerization for the first time. The effects of ionic liquids with different spatial positions, substituents and nucleophilic anions on the catalytic performance of hexafluoropropylene dimerization were systematically studied. The results showed that the strong nucleophilic trisubstituted thiocyanate imidazole ionic liquid [C6mmim][SCN] had the highest activity under the optimum reaction conditions, the turnover frequency (TOF) was 108.36 h−1 and the selectivity was 97.96%. Compared with the traditional metal salt catalyst system, the catalytic activity of ionic liquids was double. In addition, based on the XPS analysis results and density functional theory (DFT), a possible reaction mechanism was proposed. The effective catalytic activity of ionic liquids was mainly attributed to the strong nucleophilicity of anions and the weak interaction between cations and anions. This work will successfully provide a green synthesis route for hexafluoropropylene dimerization and further promote the efficiency and greening of fluorine chemical reactions.