新型双香草醛缩乙二胺铜(Ⅱ)Schiff碱配合物的制备及在Wacker反应中的应用  

A Novel Schiff Base Copper(Ⅱ)Complex:Preparation and Application in Wacker Reaction

作　　者：程庆彦[1] 杜小龙[1] 赵新强[1] 王延吉[1] 

机构地区：[1]河北工业大学绿色化工和高效节能河北省重点实验室,天津300130

出　　处：《南开大学学报（自然科学版）》2015年第3期78-85,共8页Acta Scientiarum Naturalium Universitatis Nankaiensis

基　　金：国家自然科学基金(21106030)

摘　　要：首次合成了双香草醛缩乙二胺席夫碱铜(Ⅱ)配合物(BVE-Cu).对BVE-Cu配合物进行了红外光谱、紫外光谱、热重和元素分析,并利用密度泛函理论的B3LYP方法(DFT)在高斯09程序上进行理论计算,推测出了配合物BVE-Cu的结构.将制得的席夫碱铜(Ⅱ)配合物BVE-Cu用于环己烯氧化制备环己酮的反应中,考察了其在Wacker催化体系中的性能.实验结果表明,当反应体系中无BVE-Cu时,环己酮的收率仅为17%,加入BVE-Cu后,BVE-Cu对于反应体系具有积极的作用,环己酮的收率有了明显的增加.当反应温度为30℃,反应时间为90min,高氯酸的加入量为0.08mL,BVE-Cu的加入量为0.025mmol,环己烯的加入量为0.02mL时,环己酮的收率可达58.6%.A novel bisvanillie-ethylenediamine Schiff base copper（Ⅱ）complex（BVE-Cu）has been synthesized for the first time.The structural and spectroscopic characterization of the complex BVE-Cu was determined by using both experimental methods such as elemental analysis,IR,UV-vis and thermogravimetric analysis,and quantum chemical calculations.The properties of complex BVE-Cu,as one of the part of the Wacker catalyst system,for cyclohexene to cyclohexanone has been investigated.The results showed that the yield of cyclohexanone is only 17% without BVE-Cu in the catalyst system while the yield of cyclohexanone increased obviously when BVE-Cu introduced into the catalyst system.It seemed that the Schiff base copper（Ⅱ）complex BVE-Cu played apositive role for the catalyst system.When the reaction temperature is 30 ℃,reaction time is 90 min,the amount of HClO4 is 0.08 mL,the amount of BVE-Cu is 0.025 mmol,and the amount of cyclohexene is 0.02 mL,the yield of cyclohexanone can reached 58.6%.

关 键 词：席夫碱 环己酮 量子化学计算 Wacker反应 

分 类 号：O614.121[理学—无机化学]