NHC-Ag modified samarium coordination polymer for the catalysis of terminal alkynes carboxylation with CO2
Two-dimensional coordination polymer[Sm(BCBI)(NO3)2·H2O]n(Sm-BCBI)was obtained from hydrothermal reaction of 1,3-bis(4-carboxybenzyl)-benzimidazolium chloride(H2BCBI)and Sm(NO3)3·6H2O.The N-heterocyclic carbene(NHC)-silver functionalized samarium coordination polymer[NHC-Ag(Ⅰ)@Sm-BCBI]was prepared from the interaction of Sm-BCBI and silver acetate(AgOAc),with the NHC-Ag(Ⅰ)catalytic sites introduced.Sm-BCBI and NHC-Ag(Ⅰ)@Sm-BCBI were characterized by single crystal X ray diffractometer,PXRD,TGA,XPS,inductively coupled plasma optical emission spectrometer(ICP-OES),SEM and EDS.The optimum carboxylation conditions of phenylacetylene(1.0 mmol)with CO2(0.1 MPa)catalyzed by NHC-Ag(Ⅰ)@Sm-BCBI were then investigated,and the extendibility of the substrate was further investigated.The results showed that Sm-BCBI displayed a two-dimensional layer structure,while NHC-Ag(Ⅰ)@Sm-BCBI exhibited good thermal stability with the silver in it existing in the form of +1 valence.Under the optimum reaction conditions of temperature 50℃,Cs2CO3(1.55 mmol)as base,N,N-dimethylformamide as solvent,NHC-Ag(Ⅰ)@Sm-BCB dosage 70 mg and reaction time 16 h,the separation yield of phenylpropiolic acid could reach 80%.Moreover,NHC-Ag(Ⅰ)@Sm-BCB was easy to recover,and the separation yield of phenylpropionic acid could still reach 57%after 5 times of recycling.
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