INTERACTION OF HYDRAZINE WITH COPPER(II) CHLORIDE IN ACIDIC SOLUTIONS - FORMATION, SPECTRAL AND MAGNETIC-PROPERTIES, AND STRUCTURES OF COPPER(II), COPPER(I), AND MIXED-VALENCE SPECIES
INTERACTION OF HYDRAZINE WITH COPPER(II) CHLORIDE IN ACIDIC SOLUTIONS - FORMATION, SPECTRAL AND MAGNETIC-PROPERTIES, AND STRUCTURES OF COPPER(II), COPPER(I), AND MIXED-VALENCE SPECIES
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DOI：
10.1021/ic50200a001
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发表时间：
1979-01-01
影响因子：
4.6
通讯作者：
HATFIELD, WE
中科院分区：
文献类型：
--
作者：
BROWN, DB;DONNER, JA;HATFIELD, WE
肼与氯化铜（II）在酸性水溶液中的反应已被证明产生至少四种不同的络合物。肼作为还原剂，生成白色抗磁性铜（I）络合物（N2 H4）CuCl和黑色顺磁性混合价态三铜（2 I，II）络合物（N2 H5）2Cu 3Cl 6。还形成蓝色和绿色铜（II）络合物（N2 H5）2CuCl 4·2 H2O和（N2 H5）CuCl 3。红外光谱确定了在蓝色、绿色和黑色化合物中存在配位的肼离子。所有这些材料的光谱和磁性测量的基础上提出的结构。显着的交换相互作用存在于氯化物桥接的线性链复合物（N2 H5）CliCl 3。配合物（N_2H_5）CuCl_（13）的结构已由单晶X射线计数器数据确定。该配合物在正交空间群Pnma中结晶，在尺寸为a= 14.439（2），B= 5.705（1）和c= 6.859（1）nm的晶胞中具有四个分子。该结构已被完善的全矩阵最小二乘技术，以传统的R因子（F）为0.042，使用538个独立的观察。整个分子式单元（除了一些氢原子）被限制在镜面上。该结构由二氯桥二聚体的无限链组成，其中一个氯配体用于在两个方向上传播链，而其他两个氯配体则不起作用。因此，一个氯配体与三个铜原子配位，面内距离为2.297（1）nm，两个面外距离为2.8560（5）nm，而另外两个氯配体各自仅与一个铜中心配位，键长为2.280（1）和2.298（2）nm。链中Cu-Cu'间距和Cu-Cl-Cu'桥连角分别为3.751（1）°和92.79（3）°。
The reaction of hydrazine with copper (II) chloride in acidic aqueous solution has been shown to produce at least four distinct complexes. Hydrazine behaves as a reducing agent, leading to the white, diamagnetic copper (I) complex (N2H4) CuCl and the black paramagnetic mixed-valence tricopper (2I, II) complex (N2H5) 2Cu3Cl6. Blue and green copper (II) complexes (N2H5) 2CuCl4-2H20 and (N2H5) CuCl3 are also formed. Infrared spectra establish the presence of coordinated hydrazinium ions in the blue, green, and black compounds. Structures are proposed for all of these materials on the basis of spectroscopic and magnetic measurements. Significant exchange interactions are present in the chloride-bridged linear-chain complex (N2H5) CiiCl3. The structure of the complex (N2H5) CuC13 has been determined from single-crystal X-ray counter data. The complex crystallizes in the orthorhombic space group Pnma with four molecules in a cell of dimensions a= 14.439 (2), b= 5.705 (1), and c= 6.859 (1) Á. The structure has been refined by full-matrix least-squares techniques to a conventional R factor (on F) of 0.042 using 538 independent observations. The entire formula unit (with the exception of some of the hydrogen atoms) is constrained to lie on a mirror plane. The structure consists of infinite chains of dichloro-bridgeddimers, in which one chloride ligand serves to propagate the chain in both directions while the other two chloride ligandsdo not. Thus, one chloride ligand is coordinated to three copper atoms with an in-plane distance of 2.297 (1) Á and two out-of-plane separations of 2.8560 (5) Á, while the other two chloride ligands are each coordinated to only a single copper center with bond lengths of 2.280 (1) and 2.298 (2) Á. The Cu-Cu'separation and the bridging Cu-Cl-Cu'angle in the chain are 3.751 (1) Á and 92.79 (3), respectively.