水杨醛亚胺钴(Ⅱ)配合物的合成及载氧性能  

Synthesis of Salicylaldiminate Colbet (Ⅱ) Complexes and Their Oxygen Carrying Performance

作　　者：姜翠玉 邵雪 刘蕾 梁书源 张龙力 JIANG Cuiyu;SHAO Xue;LIU Lei;LIANG Shuyuan;ZHANG Longli(College of Science,China University of Petroleum,Qingdao 266580,Shandong,China)

机构地区：[1]中国石油大学(华东)理学院

出　　处：《实验室研究与探索》2019年第12期52-56,共5页Research and Exploration In Laboratory

基　　金：山东省本科高校教学改革研究项目(B2016M009);山东省普通高等学校实验教学示范中心项目(鲁教高字[2007]6号);山东省高等学校省级教学团队(鲁教高字[2010]14号);中国石油大学(华东)教学研究与改革项目(JY-A201421);中国石油大学(华东)“大学生创新创业训练计划”项目(20171447)

摘　　要：以水杨醛及其衍生物和乙二胺、邻苯二胺为原料合成5个水杨醛亚胺(席夫碱)配体L 1~L 5,进一步与六水合硝酸钴反应合成了5个Salen Co(Ⅱ)配合物C 1~C 5,用1H NMR、IR分别对配体和配合物的结构进行表征;测定了5个Salen Co(Ⅱ)配合物的摩尔吸氧量,研究了载氧性能与结构的关系。实验结果表明:合成席夫碱的适宜条件为醛胺物质的量之比2∶1、溶剂无水乙醇用量40 mL、反应温度80℃、反应时间2.5 h,此条件下L 1产率最高,达到81.4%。在配体与硝酸钴的物质的量之比为1.5、溶剂用量为60.0 mL、反应温度80℃、反应时间3 h条件下合成5种配合物,收率皆在80%以上。Salen Co(Ⅱ)配合物载氧量由高到低的顺序为C 5>C 2>C 1>C 4>C 3,配合物的载氧量与配体取代基的电子效应、空间效应及体系的共轭程度有关,配体的电子云密度大、共轭程度高,配合物载氧量就大。Five kinds of Schiff base ligands were synthesized by salicylaldehyde and its derivatives,ethylenediamine and o-phenylenediamine.Then Salen Co(Ⅱ)complexes were synthesized with ligands L 1-L 5 and Co(NO 3)2.Ligands L 1-L 5 were characterized by 1H NMR,and metal complexes C 1-C 5 were characterized by IR spectroscopy.After that,the molar oxygen absorptions of five metal complexes were measured,and the oxygen-carrying capacity and its structure-property relationship were analyzed.The research results show that the best ratio of the salicylaldehyde to ethylenediamine is 2∶1,the solvent dosage is 40.0 mL,the reaction temperature is 80℃,and the reaction time is 2.5 h.The Schiff base ligand L 1 has the highest yield of 81.4%.Five kinds of complexes were synthesized under the conditions of a ratio of ligand to cobalt nitrate 1.5,a solvent dosage 60.0 mL,a reaction temperature 80℃,and a reaction time 3 h,and the yields were all above 80%.The molar oxygen absorption of five metal complexes from high to low is C 5>C 2>C 1>C 4>C 3,which is related to the electronic effect and steric effect of substituent in ligand,and the degree of conjugation.The electron cloud density of the ligand is larger,the degree of conjugation is higher,and the oxygen carrying capacity is larger.

关 键 词：Salen Co(Ⅱ)配合物 5-氯水杨醛 3 5-二叔丁基水杨醛 载氧性能 构效关系 

分 类 号：O641.4[理学—物理化学]