一例三(5-氯苯并噻唑-2-甲基)胺Fe(Ⅱ)配合物的串联合成过程及电催化性质研究  

Tandem synthesis process and electrocatalytic properties of a case of tris(5-chlorobenzothiazol-2-methyl)amine Fe(Ⅱ)complexes

作　　者：张琦[1] 杜静[1] 刘斌[1] ZHANG Qi;DU Jing;LIU Bin(Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials(Hubei University),Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules(Hubei University),Wuhan 430062,China)

机构地区：[1]湖北省先进有机化学材料协同创新中心(湖北大学),有机功能分子合成与应用教育部重点实验室(湖北大学),湖北武汉430062

出　　处：《湖北大学学报（自然科学版）》2024年第5期635-642,共8页Journal of Hubei University：Natural Science

基　　金：国家自然科学基金(202110601001001)资助。

摘　　要：三(芳基甲基)胺由于强配位性,在氧气活化的单/双金属非血红素金属蛋白类似物的合成中起着重要作用,且能够作为加速配体催化Click反应,因而受到广泛关注。本研究以苯并[d]噻唑-2-基甲胺(S1)和5-氯苯并[d]噻唑-2-基)甲醇(L1)为原料,在FeCl_(3)·6H_(2)O的催化下,串联合成得到了一例新颖的三(5-氯苯并噻唑甲基)胺Fe(Ⅱ)配合物1。用X-射线单晶衍射仪、X-射线粉末衍射仪、电喷雾离子化质谱确证了结构,通过晶体学和电喷雾离子质谱相结合,研究了反应过程,检测到了一系列关键中间体片段([i-Cl]^(+)、[ii+H]^(+)、[iii-Cl]^(+)),结合反应过程跟踪提出了可能的反应机理,包括N-烷基化,氧化水解等步骤,实现了3个共价键的连续构筑。对配合物1进行了OER(析氧反应)测试及稳定性性能研究,其中过电势为391 mV,Tafel斜率为95.9 mV·dec^(-1),在电极密度10 mA/cm^(2)下进行了10 h的恒电流电解,在该时间范围内稳定性良好。通过对配合物1的电催化性能研究则为后续该配体的应用领域提供一种新的方向。Tris(arylmethyl)amines have received much attention due to their strong coordination properties,their important role in the synthesis of oxygen-activated mono/bimetallic non-heme metalloprotein analogs,and their use as superior accelerating ligands to catalyze Click reactions.In the present studie,a new example of tris(5-chlorobenzothiazolylmethyl)amine Fe(Ⅱ)complex 1 was obtained by tandem reaction of benz[d]thiazol-2-ylmethylamine(S1)and 5-chlorobenzo[d]thiazol-2-yl)methanol(L1)catalyzed by FeCl_(3)·6H_(2)O.The structure of complex 1 was determanted by X-ray single-crystal diffraction,X-ray powder diffraction,and electrospray ionization mass spectroscopy(ESI-MS).Three C—N bonds were formed in complex 1.The reaction process was investigated by a combination of crystallography and ESI-MS,which detected a series of key intermediate fragments([i-Cl]^(+),[ii+H]^(+),[iii-Cl]^(+)).A possible reaction mechanism had been proposed which included N-alkylation between L1 and S1 to give secondary amine intermediate,Oxidation of the secondary amine to imine,hydorlysis of imine to give amine intermediate which realized the amino group transfer from S1 to L1,double N-alkylation of this amine intermediate with S1 to produce the complex 1.OER(oxygen evolution reaction)testing and stability performance study were conducted on complex 1.The overpotential of complex 1 was 391 mV,the Tafel slope was 95.9 mV·dec^(-1).The constant-current electrolysis was carried out at an electrode density of 10 mA/cm^(2)for 10 h,which showed good stability of complex 1 in this time range.The study of electrocatalytic properties of complex 1 provides a new direction for the subsequent application areas of this ligand.

关 键 词：串联反应 三级胺化合物 电喷雾离子化质谱 晶体学 电催化 

分 类 号：O621.22[理学—有机化学]