若干“大乌型”Schiff碱配合物合成和性质的研究  

A Study on Synthesis and Properties of Some "Big Bird" Schiff Base Complexes

作　　者：罗勤慧[1] 杨升[1] 沈孟长[1] 张正[2] 

机构地区：[1]南京大学配位化学研究所 [2]南京大学化学系

出　　处：《化学学报》1990年第4期355-359,共5页Acta Chimica Sinica

基　　金：国家自然科学基金

摘　　要：由4-叔丁基-2,6-二甲酰基苯酚与4-正己基-3-氨基硫脲缩合,合成了“大乌”配体(H_3BB).它与Cu(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)、Pb(Ⅱ)、Cd(Ⅱ)生成五种电中性的可溶性“大乌”配合物.除Co(Ⅱ)配合物外,其余四种均为乙氧基桥联的双核配合物.配体是将4-叔丁基-2,6-二羟甲基苯酚用MnO_2在室温下直接氧化,得到4-叔丁基-2,6-二甲酰基苯酚,然后再与4-正己基-3-硫代氨基脲缩合而得,该反应步骤较少,产量较高,优于前人结果.用IR、UV等方法对配合物进行了表征,并用Evans的核磁共振法研究了吡啶与Ni_2BB(0Et)在轴向的作用和配合物两中心原子间的作用.这五种配合物中,有趣的是Ni_2BB(OEt)呈顺磁性,本文对其原因作了探讨.Big Bird ligand (H_3BB) was synthesized by condensation of 4-burt-butyl-2,6-diformyl phenol with 4-n-hexyl-3-thio-aminourea.Five new electroneutral and soluble big bird complexes of Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), Pb(Ⅱ) and Cd(Ⅱ) were synthesized.Except Co(Ⅱ) complex,all of them are binuelear complexes with ethoxy-bridge (M_2BB (OEt)].The ligand was prepared by treating 4-tert-butyl-2,6-dihydroxymethyl phenol with active MnO_2 directly at room temperature to give 4-tert-butyl-2,6-diformyl phenol,which is then condensed with 4-n-hexyl-3-thio-semicarbazide.The procedure has higher yield and fewer steps than that of previous method. We characterized big bird complexes by IR and UV-Vis spectroscopy and studied the interaction of pyridine with Ni_2BB(OEt) in axial direction and that between two central metal atoms in eomplex by Evans' NMR method.It is interesting that the complex Ni_2BB (OEt) is paramagnetic,the possible reason was discussed.

关 键 词：大乌型 SCHIFF碱 配合物 合成 

分 类 号：O641.4[理学—物理化学]