N_2O_2型Schiff碱配体和锰(Ⅲ)配合物的合成与光谱表征

Synthesis and Spectroscopic Properties of Tetradentate Schiff Base Ligands Coordinate to Manganese (Ⅲ)

报道了８ 个水杨醛及邻香草醛与二胺缩合生成的Ｓｃｈｉｆｆ碱与锰（Ⅲ）的配合物：［Ｍｎ（ｓａｌｐｎ）Ｃｌ］，［Ｍｎ（ｓａｌｉｐｎ）Ｃｌ］，［Ｍｎ（ｖａｎｉｐｎ）Ｃｌ］，［Ｍｎ（ｓａｌｅｎ）（Ｈ２Ｏ）］ＣｌＯ４，［Ｍｎ（ｖａｎｅｎ）（Ｈ２Ｏ）２］２（ＣｌＯ４）２（Ｈ２Ｏ）２，［Ｍｎ（ｖａｎｉｐｎ）（Ｈ２Ｏ）２］２（ＣｌＯ４）２（Ｈ２Ｏ）２，［Ｍｎ（ｓａｌｅｎ）（ＮＣＳ）］，［｛Ｍｎ（ｏｓａｌｐｈｅｎ）（ＮＣＳ）｝｛Ｍｎ（ｓａｌｐｈｅｎ）（ＮＣＳ）（ＤＭＦ）｝］（其中ｓａｌ为水杨醛，ｖａｎ 为邻香草醛，ｅｎ 为乙二胺，ｐｎ 为１，３丙二胺，ｉｐｎ 为１，２丙二胺，ｏｐｈｅｎ 为邻苯二胺）．对所有的配合物进行了元素分析．对配合物中的ν（Ｃ＝ Ｎ），δ１（ＣＨ３，ＣＨ２），δ２（ＣＨ３，ＣＨ２），ν（Ｃ－ Ｎ），ν（Ｃ＝ Ｃ），ν（Ｍｎ－ Ｏ）以及ＤＭＦ和ＣｌＯ－４ 、ＮＣＳ－ 的振动吸收进行了归属．紫外光谱测试表明，配合物中存在着芳环的π→π，金属到配体的ＣＴ电荷转移跃迁，Ｃ＝ Ｎ的π→π以及ｄ→π跃迁．磁距测定表明，配合物的中心离子为ｄ４ 锰（Ⅲ）高自旋的电子结构．

new N 2O 2 type tetradentate Schiff base manganese(Ⅲ) complexes,[Mn(salpn)Cl],[Mn(salipn)Cl],[Mn(vanipn)Cl],[Mn(salen)(H 2O)]ClO 4,[Mn(vanen)(H 2O) 2] 2(ClO 4) 2(H 2O) 2,[Mn(vanipn)(H 2O) 2] 2(ClO 4) 2(H 2O) 2,[Mn(salen)(NCS)],[｛Mn( o salphen)(NCS)｝｛Mn(salphen)(NCS)(DMF)｝] (sal=salicylaldehyde, van= o vaniline, en=1,2 diaminoethane, pn=1,3 diaminopropane, ipn=1,2 diaminopropane, and phen= o phenyldiamine) were synthesized and characterized by an elemental analysis. The IR vibration absorption peaks of ν (C=N), δ 1 (CH 3,CH 2), δ 2 (CH 3,CH 2), ν (C-N), ν (C=C), ν (Mn-O) as well as DMF, ClO - 4, and NCS - were assigned. In the complexes, there are π→π *(C=N), π→π *(phenyl), CT and d→π * transitions as are confirmed by UV visible spectra. Magnetic measurements on these complexes reveal room temperature magnetic moments close to 4.90 μ B consistent with a high spin d 4 system with no magnetic interaction between the manganese centers.