NHC-Ag修饰的钐配合物催化CO_(2)与端炔的羧化反应  

NHC-Ag modified samarium coordination polymer for the catalysis of terminal alkynes carboxylation with CO_(2)

作　　者：李金融 王文玉 王晓娟 由立新[1] 熊刚[1] 孙亚光[1] LI Jinrong;WANG Wenyu;WANG Xiaojuan;YOU Lixin;XIONG Gang;SUN Yaguang(College of Science,Shenyang University of Chemical Technology,Shenyang 110142,Liaoning,China)

机构地区：[1]沈阳化工大学理学院,辽宁沈阳110142

出　　处：《精细化工》2024年第4期865-871,共7页Fine Chemicals

基　　金：辽宁省教育厅科学研究经费项目(LJKZ0432)。

摘　　要：将1,3-二(4-羧基苯甲基)-苯并咪唑氯化物(H_(2)BCBI)与Sm(NO_(3))3•6H_(2)O在水热条件下进行反应,得到了二维配位聚合物[Sm(BCBI)(NO_(3))2•H_(2)O]n(Sm-BCBI),将其与乙酸银(AgOAc)作用引入氮杂环卡宾(NHC)-Ag(Ⅰ)催化位点,制备了氮杂环卡宾-银功能化的钐配合物[NHC-Ag(Ⅰ)@Sm-BCBI]。通过单晶X射线衍射仪、PXRD、TGA、XPS、电感耦合等离子发射光谱仪、SEM和EDS对Sm-BCBI和NHC-Ag(Ⅰ)@Sm-BCBI进行了表征,考察了NHC-Ag(Ⅰ)@Sm-BCBI催化CO_(2)(0.1MPa)与苯乙炔(1.0mmol)羧化反应的最佳条件,考察了底物的拓展性。结果表明,Sm-BCBI为二维层状结构;NHC-Ag(Ⅰ)@Sm-BCBI具有良好的热稳定性,且其中的银以+1价形式存在。在反应温度为50℃、以Cs2CO_(3)(1.5 mmol)为碱、N,N-二甲基甲酰胺为溶剂,NHC-Ag(Ⅰ)@Sm-BCB用量70 mg、反应时间为16h的最佳条件下,苯丙炔酸分离产率可达80%。催化剂易回收,循环使用5次后,苯丙炔酸分离产率仍能达到57%。Two-dimensional coordination polymer[Sm(BCBI)(NO_(3))2•H_(2)O]n(Sm-BCBI)was obtained from hydrothermal reaction of 1,3-bis(4-carboxybenzyl)-benzimidazolium chloride(H_(2)BCBI)and Sm(NO_(3))3•6H_(2)O.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 CO_(2)(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℃,Cs2CO_(3)(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.

关 键 词：氮杂环卡宾-银 催化 CO_(2) 端炔 羧化反应 

分 类 号：X701[环境科学与工程—环境工程] TQ426[化学工程] O641.4[理学—物理化学]