NHC-Ag修饰的钐配合物催化CO2与端炔的羧化反应
NHC-Ag modified samarium coordination polymer for the catalysis of terminal alkynes carboxylation with CO2
李金融 1王文玉 1王晓娟 1由立新 1熊刚 1孙亚光1
作者信息
- 1. 沈阳化工大学 理学院,辽宁沈阳 110142
- 折叠
摘要
将1,3-二(4-羧基苯甲基)-苯并咪唑(鎓)氯化物(H2BCBI)与Sm(NO3)3·6H2O在水热条件下进行反应,得到了二维配位聚合物[Sm(BCBI)(NO3)2·H2O]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CO2(0.1 MPa)与苯乙炔(1.0 mmol)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Cs2CO3(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16 h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%.
Abstract
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.
关键词
氮杂环卡宾-银/催化/CO2/端炔/羧化反应Key words
N-heterocyclic carbene-Ag/catalysis/CO2/terminal alkynes/carboxylation reaction引用本文复制引用
基金项目
辽宁省教育厅科学研究经费项目(LJKZ0432)
出版年
2024
NETL
NSTL
万方数据