| 对称性破缺：手性高氯酸乙酸·二(乙二胺)合锌(Ⅱ)的合成与结构 |
| Symmetry Breaking：Synthesis, Crystal Structure of Chiral Acetatobis(diaminoethane)zinc(Ⅱ) Perchlorate |
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| 摘要: 用简单的非手性原料醋酸锌和乙二胺在高氯酸钠的甲醇溶液中反应，反应过程中发生了对称性破缺现象，得到了一对对映体Δ-cis-[Zn(en)2Ac][ClO4](Δ-1)and Λ-cis-[Zn(en)2Ac][ClO4](Λ-1)(en=乙二胺，Ac-=醋酸根)。用元素分析、红外光谱、CD光谱和X-ray单晶衍射对产物进行了表征。X-ray单晶衍射结果表明配合物Δ-1和Λ-1中的锌(Ⅱ)离子均与2个乙二胺上的4个氮原子和醋酸根上的2个氧原子顺式配位，形成六配位畸变的八面体构型。{Δ-cis-[Zn(en)2Ac]}+和{Λ-cis-[Zn(en)2Ac]}+单体通过氢键作用分别形成具有右手和左手双螺旋的一维链。用X-ray单晶衍射和CD光谱确定了配合物的手性特征。 |
| 关键词: 对称性破缺 锌配合物 晶体结构 CD光谱 手性 |
| 基金项目: 湖南省大学生研究性学习和创新性实验计划(No.2013-191)，湖南省教育厅项目(No.13B029，13A030)，湖南省“十二五”重点建设学科(No.2011-76)，湖南省科技创新团队(No.2012-318)，湖南省科技计划(No.2013FJ3004)和湖南科技学院英才计划资助项目。 |
| Abstract: The reaction of zinc acetate with diaminoethane and sodium perchlorate gave two chiral complexes Δ-cis-[Zn(en)2Ac][ClO4] (Δ-1) and Λ-cis-[Zn(en)2Ac][ClO4] (Λ-1)(en=diaminoethane, Ac-=Acetic anion) in the absence of any chiral source, and the spontaneous chiral symmetry breaking occurs during the reaction. The products were characterized by elemental analysis, IR, circular dichroism (CD) spectra. Single crystal X-ray diffraction analyses indicated that the central Zn(Ⅱ) atoms in Δ-1 and Λ-1 display a distorted six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms of two diaminoethane ligands, and two oxygen atoms of Ac- in the cis-position. It was found that the monomers of {Δ-cis-[Zn(en)2Ac]}+ and {Λ-cis-[Zn(en)2 Ac]}+ are connected through the intermolecular hydrogen bonds to generate one-dimensional double-stranded chains with right-handed and left-handed double-helicity. The chiral natures of Δ-1 and Λ-1 are confirmed by the results of X-ray diffraction and CDspectra measurements. CCDC: 957460, Δ-1; 957461, Λ-1. |
| Keywords: symmetry breaking zinc(Ⅱ) complex crystal structure CD spectra chirality |
| 投稿时间：2013-10-08 修订日期：2013-12-14 |
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| 欧光川,李治章,张敏,袁先友.对称性破缺：手性高氯酸乙酸·二(乙二胺)合锌(Ⅱ)的合成与结构[J].无机化学学报,2014,30(6):1459-1463. |
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| Support information: 相关附件： file130754_Supporting+Information.pdf |
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