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用直接合成法合成了一种新配体-1,7-N,N′-二(邻氨基苯基)-1,7-二氮杂-4,10-二氧杂环十二烷[L]。经元素分析~1H、~(13)C核磁共振、质谱、红外光谱等分析证实了其结构。并藉该配体合成了Cu(Ⅱ),Cd(Ⅱ),Ag(Ⅰ),Ni(Ⅱ)四种固体配合物。经元素分析配合物的组成分别为:[CuCl_2]_2·L,[CdCl_2]_2·2L·2H_2O_2[AgNO_3]_2·L,[NiCl_2]_2·L·H_2O.对配合物进行了红外光谱、紫外光谱、摩尔电导和差热分析。配合物的红外特征吸收峰均有明显位移或分裂;紫外特征吸收峰稍有位移。但摩尔吸光系数改变很大;摩尔电导表明配合物为1:1或接近2:1型电解质;差热分析表明配合物的热稳定性顺序为:Cd(Ⅱ)、Ni(Ⅱ)>Cu(Ⅱ)>Ag(Ⅰ)。对Cu(Ⅱ)配合物进行了ESR谱分析,并且对甲醇溶液中Cu(Ⅱ)与配体(L)的掺入反应动力学进行了初步研究,结果表明,掺入反应为典型的二级反应。
A novel ligand, 1, 7-N, N’-bis (o-aminophenyl) -1,7-diaza-4,10-dioxacyclododecane [L ]. The structure was confirmed by elemental analysis ~ 1H, ~ (13) C NMR, MS and IR spectra. Four solid complexes of Cu (Ⅱ), Cd (Ⅱ), Ag (Ⅰ) and Ni (Ⅱ) were synthesized by this ligand. The composition of the complex was: [CuCl_2] _2 · L, [CdCl_2] _2 · 2L · 2H_2O_2 [AgNO_3] _2 · L, [NiCl_2] _2 · L · H_2O. The IR, UV Spectra, Molar Conductivity and Differential Thermal Analysis. The infrared absorption peaks of the complexes all have obvious displacement or splitting; the UV absorption peaks are slightly shifted. But the molar extinction coefficient changed greatly. The molar conductance showed that the complex was 1: 1 or nearly 2: 1 type electrolyte. The thermal analysis showed that the thermal stability of the complex was Cd (Ⅱ), Ni (Ⅱ)> Cu Ⅱ)> Ag (Ⅰ). The ESR spectra of Cu (Ⅱ) complexes were studied, and the kinetics of Cu (Ⅱ) and L (subscript L) incorporation reaction in methanol solution was studied. The results showed that the incorporation reaction was a typical secondary reaction.