基于苯磺酸配体构筑的Cu(Ⅱ)配合物的合成、表征及催化性能  

Synthesis,Characterization and Catalytic Property of the Cu(Ⅱ)Complex Based on Benzene Sulfonic Acid Ligand

作　　者：王鑫[1] 祁金阳 杨瑞杰 宋志国[1] 王敏[1] WANG Xin;QI Jinyang;YANG Ruijie;SONG Zhiguo;WANG Min(College of Chemistry and Materials Engineering,Bohai University,Jinzhou 121013,China)

机构地区：[1]渤海大学化学与材料工程学院,锦州121013

出　　处：《高等学校化学学报》2024年第10期9-18,共10页Chemical Journal of Chinese Universities

基　　金：教育部产学合作协同育人项目2024年第一批次(批准号:230805940290824)资助。

摘　　要：以三水合硝酸铜、对甲基苯磺酸钠(p-CH_(3)C_(6)H_(4)SO_(3)Na)和咪唑(Im)为原料,利用溶剂热合成法制备了配合物Cu(Im)_(4)(p-CH_(3)C_(6)H_(4)SO_(3))_(2).通过单晶X射线衍射分析、红外光谱、热重分析、氮气吸附/脱附分析及粉末X射线衍射分析对其进行了表征.由单晶X射线衍射分析可知,该配合物的中心Cu^(2+)与2个对甲基苯磺酸根中的O原子和4个咪唑的N原子配位,通过分子间氢键作用力形成了三维网状结构.以Knoevenagel缩合反应为探针对配合物的催化性能进行了考察,结果表明,该配合物在Knoevenagel缩合反应中具有酸碱协同催化作用,反应时间短,产品产率高,且催化剂可多次重复使用.最后,通过密度泛函理论(DFT)对Cu(Im)_(4)(p-CH_(3)C_(6)H_(4)SO_(3))_(2)、苯甲醛和丙二腈进行了量化计算,预测了活性位点和反应位点;并利用X射线光电子能谱进行了验证,进而推测出可能的催化作用机理.Cu(Im)_(4)(p-CH_(3)C_(6)H_(4)SO_(3))_(2) was prepared by solvent thermal synthesis using copper nitrate trihydrate,sodium p-methylbenzenesulfonate(p-CH_(3)C_(6)H_(4)SO_(3)Na)and imidazole(Im)as raw materials.It was characterized by means of single crystal X-ray diffraction,infrared spectroscopy,thermogravimetric analysis,nitrogen adsorption/desorption analysis and powder X-ray diffraction.By single crystal X-ray diffraction analysis,it could be seen that the center Cu^(2+)of the complex was coordinated with O atoms in two p-methylbenzenesulfonate anions and N atoms in four imidazoles to form a three-dimensional network structure by intermolecular hydrogen bonding force.The Knoevenagel condensation reaction was used as a probe to investigate the catalytic activity of the complex.The results showed that the complex exhibited acid-base synergistic catalysis in the Knoevenagel condensation reaction.The reaction time was short,the products yields were high,and the catalyst could be reused many times.Finally,the activity sites and reaction sites of Cu(Im)_(4)(p-CH_(3)C_(6)H_(4)SO_(3))_(2),benzaldehyde and malononitrile were predicted by density functional theory(DFT)and verified by X-ray photoelectron spectroscopy,and the possible catalytic mechanism was deduced.

关 键 词：苯磺酸配合物 KNOEVENAGEL缩合反应 酸碱协同催化 密度泛函理论 催化机理 

分 类 号：O614.1[理学—无机化学]