Metal Complexes with Macrocyclic Ligands Part XXX†. Synthesis and structure of halocuprates of tetraprotonated 1,4,8,11-tetraazacyclotetradecane and its Cu2+ complex
Metal Complexes with Macrocyclic Ligands Part XXX†. Synthesis and structure of halocuprates of tetraprotonated 1,4,8,11-tetraazacyclotetradecane and its Cu2+ complex
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具有大环配体的金属络合物第 XXX 部分†。四质子化 1,4,8,11-四氮杂环十四烷及其 Cu2+ 络合物的合成和结构。
DOI：
10.1002/hlca.19890720610
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发表时间：
1989
期刊：
影响因子：
--
通讯作者：
T. Kaden
中科院分区：
文献类型：
--
作者：
M. Studer;A. Riesen;T. Kaden
通过将1，4，8，11-四氮杂环十四烷（Cy）的酸性溶液与CuX 2（X = Cl-、Br-）混合，得到大环四质子化形式的六卤铜酸盐（[CyH 4] [CuX 6]）或其Cu 2+配合物的四卤铜酸盐（[CuCy] [CuX 4]）。氯代衍生物的结构通过X-射线衍射分析确定。在[CyH 4] [CuCl 6]中，Cu 2+为四面体畸变八面体构型，具有四个短CuCl键和两个长CuCl键。四质子化的大环是中心对称的，其构象是外齿的，因此四个铵基彼此尽可能远离以使静电排斥最小化。在[CuCy] [CuCl 4]中，由大环络合的Cu 2+离子被四个正方形平面排列的N-原子包围。此外，轴向位置被两个CuCl单元的两个Cl-离子占据，它们充当桥梁。大环为反式-III-构型。另一个Cu 2+离子与四个Cl−离子配位，形成扭曲的四面体构型。利用氯代和溴代衍生物的红外光谱和维斯光谱讨论了溴代物种的结构。
By mixing acidic solutions of 1,4,8,11-tetraazacyclotetradecane (Cy) with CuX2 (X = Cl−, Br−), either the hexahalocuprates of the tetraprotonated form of the macrocycle ([CyH4] [CuX6]) or the tetrahalocuprates of its Cu2+ complex ([CuCy] [CuX4]) are obtained. The structures of the chloro derivatives are established by X-ray diffraction analysis. In [CyH4] [CuCl6], the Cu2+ is in a tetragonally distorted octahedral geometry with four short and two long CuCl bonds. The tetraprotonated macrocycle is centrosymmetric, and its conformation is exodentate, so that the four ammonium groups are as far as possible from each other to minimize the electrostatic repulsion. In [CuCy] [CuCl4], the Cu2+ ion complexed by the macrocycle is surrounded by four N-atoms in a square-planar arrangement. In addition, the axial positions are occupied by two Cl− ions of two CuCl units, which act as bridges. The macrocycle is in the trans-III-configuration. The other Cu2+ ion is coordinated by four Cl− ions in a distorted tetrahedral geometry. IR and VIS spectra of the chloro and bromo derivatives are used to discuss the structure of the bromo species.