N,N,N-三齿席夫碱铜(Ⅱ)配合物的合成、晶体结构及儿茶酚酶活性  

Synthesis,Crystal Structure and Catecholase Activity of Copper(Ⅱ)Complexes with N,N,N⁃Tridentate Schiff Base Ligand

作　　者：白一泽 刘睿端 鲁秋然 赵海燕[1] BAI Yize;LIU Ruiduan;LU Qiuran;ZHAO Haiyan(School of Sciences,Hebei University of Science and Technology,Shijiazhuang 050018,China)

机构地区：[1]河北科技大学理学院,石家庄050018

出　　处：《高等学校化学学报》2024年第7期27-36,共10页Chemical Journal of Chinese Universities

基　　金：河北省自然科学基金重点项目(批准号:B2020208095);河北省大学生创新创业训练计划(批准号:S202210082043)资助.

摘　　要：选用N,N,N-三齿席夫碱化合物2-氨基乙基苯并咪唑缩吡啶-2-甲醛(L^(1))和2-氨基丙基苯并咪唑缩吡啶-2-甲醛(L^(2))为配体,与过渡金属Cu(Ⅱ)盐反应合成了4个单核铜配合物:[Cu(L^(1))Cl_(2)](1),[Cu(L^(1))(SCN)_(2)](2),[Cu(L^(1))bpy](ClO_(4))_(2)·CH_(3)OH(3)和[Cu(L^(2))bpy](ClO_(4))_(2)(4)(bpy=2,2′-联吡啶).通过元素分析、红外光谱、粉末X射线衍射、单晶X射线衍射、热重分析和循环伏安分析等手段对配合物进行了表征.结果表明,在固体状态下,配合物1~4均为单核Cu(Ⅱ)配合物,中心Cu(Ⅱ)均为畸变四方锥构型,结构参数τ=0.088~0.340.以3,5-二叔丁基邻苯二酚为底物,研究了配合物1~4模拟儿茶酚氧化酶的催化活性,采用Michaelis-Menten模型和Lineweaver-Burk图法计算了动力学参数.结果表明,配合物均具有儿茶酚氧化酶活性,催化活性顺序为2>3≈4>1,氧化速率取决于Cu(Ⅱ)配位环境的畸变程度、离去基团与中心Cu(Ⅱ)的键长和配合物的空间位阻.Four complexes,[Cu(L^(1))Cl_(2)](1),[Cu(L^(1))(SCN)_(2)](2),[Cu(L^(1))bpy](ClO_(4))_(2)·CH_(3)OH(3)and[Cu(L^(2))bpy](ClO_(4))_(2)(4),were synthesized via the reaction of the N,N,N-tridentate Schiff base ligands,2-[(1H-benzimidazol-2-yl-ethylimino)-methyl]pyridine(L^(1))or 2-[(1H-benzimidazol-2-yl-propylimino)-methyl]pyridine(L^(2))with Cu(Ⅱ)salts(where bpy=2,2′-bipyridine).The complexes were characterized by means of elemental analysis,infrared spectroscopy,powder X-ray diffraction,single-crystal X-ray diffraction,thermal gravimetric analysis and cyclic voltammetry.In the solid state,complexes 1~4 are mononuclear Cu(Ⅱ)complexes and the Cu(Ⅱ)ions exhibit distorted square pyramidal coordination geometry withτvalues ranging from 0.088 to 0.340.Catecholase activity of the complexes has been studied using 3,5-di-tertbutyl catechol(3,5-DTBC)as model substrate,and kinetic parameters were calculated using the Michaelis-Menten model and Lineweaver-Burk plot.The results demonstrate that all complexes exhibit catecholase activity,with the catechol oxidation rates following the order of 2>3≈4>1.The oxidation rates depend on the distortion of the Cu(Ⅱ)coordination environment,the bond lengths of the leaving group of Cu(Ⅱ)ions and the steric hindrance of the complexes.

关 键 词：席夫碱 Cu(Ⅱ)配合物 晶体结构 儿茶酚氧化酶活性 

分 类 号：O614[理学—无机化学]