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

Abstract

Ionic liquids, as an efficient nucleophilic catalyst, is used for the first time in the dimerization of perfluoroolefin, and further promotes the greening of fluorochemical reactions.

Efficient dimerization of perfluoroolefin catalyzed by strong nucleophilic bifunctional ionic liquids

“…Notably, under the same conditions, the traditional KF/crown ether system showed lower activity and that the catalytic activity of ionic liquid with [C 4 Mpyrr] + , [C 4 DMAP] + , [C 4 DMEA] + , and [C 3 OHDMAP] + as cations was higher than that of [C 4 Mmim][SCN] ionic liquid catalysts reported in the literature. 18 The results also indicated that [C 4 Py][SCN] was consistent with literature reports, and this result was related to the active hydrogen at the 4-position of pyridine. 29…”

“…According to our previous experience, among the studies comparing the impact of various common anions on hexafluoropropylene dimerization reactions, it was established that the SCN − anion exhibits strong nucleophilic characteristics and delivers the most effective catalytic performance. 18 Consequently, the anions for the synthesized ionic liquids were standardized as SCN − . Firstly, the effects of different cationic head groups on the catalytic performance of hexafluoropropylene dimerization were investigated.…”

“…Deuterated trifluoroacetic acid was used as a solution, and the structure of the main products was analyzed using a NMR spectrometer. The turnover frequency (TOF) values and selectivity of product D 1 were determined and calculated using eqn (1) and (2): 18 where N D1 , N D2 , and N T are the amount of substances D1 (perfluoro(4-methyl-2-pentene)), D2 (perfluoro-2-methyl-2-pentene), and T (hexafluoropropylene trimer) and after the reaction, and N Catalyst is the amount of catalyst.…”

“…Nucleophilic ionic liquids, designed specifically for enhancing hexafluoropropylene dimerization reactions, have shown promising results. For instance, Huang et al 18 reported the use of methyl-substituted imidazole ionic liquids featuring strong nucleophilic anions for hexafluoropropylene dimerization. The optimal catalyst demonstrated twice the efficiency of conventional metal salt catalyst systems, boasting a turnover frequency (TOF) of 108.36 h −1 and 97.96% selectivity for D1.…”

De novo assembly of frustrated Lewis pair bearing metal‐organic frameworks for atmospheric CO2 cycloaddition

“…We herein propose a strategy of capping Lewis-base-functionalized monodentate ligands on the metal centers during the de novo synthesis of MOFs, by which the adjacent metal sites turn coordinatively unsaturated and then generate FLPs with the incorporated Lewis basic molecules. Considering that ionic liquids (ILs) are high-efficiency Lewis basic molecular catalysts by virtue of their intrinsic nucleophilic anions (e.g., halide ions) and tailored acidity/basicity, 16,17 we have designed a kind of monocarboxyl functionalized ILs as monodentate ligands. Based on the bottom-to-up assembly strategy, ILs are distributed on the framework to ensure large specific surface areas, open porous channels, and good thermostability, and FLP nanospaces consisted of ILs and unsaturated metal sites are constructed (Figure 1A).…”