基于共轭驱动的Cu(Ⅱ)氧化仲胺合成氯桥联双核Cu(Ⅰ)配合物  

Synthesis of Chlorine-Bridged Binuclear Cu(I)Complexes Based on Conjugation-Driven Cu(II)Oxidized Secondary Amines

作　　者：张永坡[1] 李鑫峰 宋亚菲 孙萌瑶 殷丛丛 高春艳[1] 赵晋忠[1] Yongpo Zhang;Xinfeng Li;Yafei Song;Mengyao Sun;Congcong Yin;Chunyan Gao;Jinzhong Zhao(Department of Basic Science,Shanxi Agricultural University,Jinzhong 030801,Shanxi Province,China)

机构地区：[1]山西农业大学基础部,山西晋中030801

出　　处：《大学化学》2024年第5期44-51,共8页University Chemistry

基　　金：山西省高等学校教学改革创新项目(J2021226,J20230379,J20230434,J20220251)。

摘　　要：现行的实验教材中缺乏双核桥联配合物合成的实验,关于仲胺合成和Cu(Ⅱ)氧化性的知识也较少。本实验从有机化学理论知识中的基本反应出发,设计了两条路线合成目标仲胺配体,即基于亲核取代反应的路线一和亲核加成缩合-还原的路线二。运用配位化学原理及有机化学中的共轭驱动效应,使弱氧化性的Cu(Ⅱ)将仲胺氧化成共轭的芳香亚胺(希夫碱)结构,同时利用希夫碱的配位作用和氯离子的桥联配位作用形成稳定的氯桥联双核Cu(Ⅰ)配合物。为适应普通高校的实验教学条件,本实验还设计了一套操作简单、现象直观的Cu(Ⅰ)配合物中铜离子价态的鉴定实验。本实验所涉实验原理既包含基础化学反应知识,又体现最新的科学研究成果,反应条件温和、实验现象直观、重现性好、收率高,能有效提高学生的综合实验操作技能,锻炼学生的有机合成、配位合成能力。There is a dearth of experiments on the synthesis of binuclear bridging complexes in current experimental textbooks,and limited knowledge exists regarding secondary amine synthesis and Cu(II)oxidation.In this study,drawing from the foundational reactions in organic chemistry theory,two routes were devised to synthesize the target secondary amine ligand.Route 1 is predicated on nucleophilic substitution reactions,while Route 2 involves nucleophilic addition condensation and reduction.Leveraging the principles of coordination chemistry and the conjugated drive effect in organic chemistry,Cu(II),with its weak oxidizing properties,oxidized secondary amines into conjugated aromatic imines(Schiff base)structures.Concurrently,the coordination of Schiff base and the bridging coordination of chloride ions were harnessed to form stable chlorine-bridged binuclear Cu(I)complexes.To suit the experimental teaching conditions in tertiary institutions,a straightforward operational set-up was designed to visually illustrate the identification of copper ion valence states in Cu(I)complexes.The experimental principles herein encompass not only fundamental chemical reaction knowledge but also embody the latest scientific research findings.With mild reaction conditions,intuitive experimental observations,good reproducibility,and high yields,this experiment effectively enhances students’comprehensive experimental operation skills and cultivates their abilities in organic synthesis and coordination chemistry.

关 键 词：双核配合物 桥联 仲胺 氧化还原反应 亚铜 

分 类 号：G64[文化科学—高等教育学] O4[文化科学—教育学]