Cu(I) or Cu(I)-Cu(II) mixed-valence complexes of 2,4,6-Tri(2-pyridyl)-1,3,5-triazine: syntheses, structures, and theoretical study of the hydrolytic reaction mechanism.
Cu(I) or Cu(I)-Cu(II) mixed-valence complexes of 2,4,6-Tri(2-pyridyl)-1,3,5-triazine: syntheses, structures, and theoretical study of the hydrolytic reaction mechanism.
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DOI：
10.1021/ic060564p
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发表时间：
2006-08
影响因子：
4.6
通讯作者：
Xiao‐Ping Zhou;Dan Li;Shao-Liang Zheng;Xuanjun Zhang;Tao Wu
中科院分区：
文献类型：
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作者：
Xiao‐Ping Zhou;Dan Li;Shao-Liang Zheng;Xuanjun Zhang;Tao Wu
2，4，6-三(2-吡啶基)-1，3，5-三嗪(TPT)与卤化铜(I)在溶剂热或传统条件下反应生成两个聚合物铜(I)配合物[Cu2I2(TPT)]n(1)和[Cu3I3(TPT)]n(2)，一个混价铜(I)-铜(II)配合物[Cu4Cl2I4(TPT)2](3)和两个铜(II)配合物[CuBr(BPCA)](4)和[CuI(BPCA)](5)(BPCA=双(2-吡啶甲酰)胺)。配合物1与TPT以双联吡啶配位方式形成锯齿状链状结构，而配合物2与TPT与3个铜(I)离子形成梯形配位聚合物。配合物3为混价结构，其中铜(I)为扭曲的四面体构型，而铜(II)为扭曲的正方形锥形构型，形成梯形超分子链。络合物4和5是TPT原位水解的产物，涉及铜(I)的氧化。配合物1、2和5的合成和表征表明，铜(I)不能促进TPT的水解。理论研究表明，金属离子的吸电子效应是影响TPT水解的主要因素。
The reactions of 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tpt) with copper(I) halides under solvothermal or traditional conditions yielded two polymeric Cu(I) complexes [Cu2I2(tpt)]n (1) and [Cu3I3(tpt)]n (2), one mixed-valence Cu(I)-Cu(II) complex [Cu4Cl2I4(tpt)2] (3), and two Cu(II) complexes [CuBr(bpca)] (4) and [CuI(bpca)] (5) (bpca = bis(2-pyridylcarbonyl)amine). Complex 1 is a zigzag chain with tpt in a bis-bipyridine-like coordination mode, whereas complex 2 with tpt chelating three Cu(I) cations is a ladderlike coordination polymer. Complex 3 is mixed-valence, with Cu(I) in a distorted tetrahedral geometry and Cu(II) in a distorted square pyramidal geometry, forming a ladderlike supramolecular chain. Complexes 4 and 5 are the products of in situ hydrolysis of tpt involving the oxidation of Cu(I). The synthesis and characterization of complex 1, 2, and 5 indicated that Cu(I) cannot promote the hydrolysis of tpt. The theoretical study shows that the main effect for hydrolysis of tpt is the electron-withdrawing effect of metal ions.