Stereo molecular structures around each metal atom of planar metal complexes in solution analyzed by the combination of some instrumental analyses

通过结合一些仪器分析来分析溶液中平面金属配合物的每个金属原子周围的立体分子结构

基本信息

批准号：
11640618
负责人：
WAKITA Hisanobu
金额：
$ 1.98万
依托单位：
Fukuoka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

To analyze stereo molecular structures around each metal atom of planar metal complexes in solution which are related to the character of their complexes in solution, we mainly have measured XANES spectra of them, established the spectral analysis method using a DV-Xα molecular orbital calculation method, and clarified the relationship between their structures and chemical characters. The copper (II) complex of (N,N', N", N'''-tetrakis (2-aminoethyl)-1,4,8,11-tetraazacyclotetradecane) forms a dinuclear structure in crystal. If Br^- is a counter anion this complex forms a bridged structure, and forms an unbridged one if ClO_4^- is a counter anion. To discuss the behavior of the complex in solution, we measured XANES spectra of this complex in crystal and in aqueous solution and analyzed the spectra with a DV-Xα method. In case of the Br^- bridged complex, there is no change between both spectra. However, in case of the unbridged complex, the XANES spectra of the complex in aqueous solut … More ion show the clear difference with the spectra of the complex in crystal. The DV-Xα calculation for both spectra clarified that the complexes in aqueous solution form a bridged structure by Br^- or oxygen atom (one oxygen atom in ClO_4^- anion). Bis (1,2-dione diozimato) nickel (II) complexes form two different types of one dimensional stacking structures. The crystal samples of the complexes give two different type XANES spectra, however, the pyridine solution samples of them give only the same spectra. We analyzed those spectra by our DV-Xα calculation method using proposed model structures, and clarified the spectral change, between them. In case of solid samples the spectral change at about 8340eV shows the difference between each atomic interaction in their stacking structures, and in case of pyridine solution samples the complexes give the only one structure which the complex molecules are stacked one above the other, although adjacent molecules in the stacking structures slightly deviate from the c axis. The result gives good information for the origin of red color of the complex solution. [CuBr_2(cyclam)] and [Cu(cyclam)(H_2O)_2]F_2-4H_2O are two different type complexes of cyclam, 1,4,8,11-tetraaza cyclotetradencane, and the XANES spectra of these complexes in solid and solution are different with each other. We analyzed the spectra using our DV-Xα method, and the results suggest that the different spectral patterns are caused by exchanging one axial Br^- with an H_2O molecule to Cu(II) in aqueous solution and the predominant complex in aqueous solution is [CuBr(cyclam)(H_2O)]^+. The upper mentioned studies show XANES spectral analysis by our DV-Xα calculation method is very effective method for analyzing stereoscopic inter-atomic interactions in solid and in solution. Less

为了分析溶液中平面金属复合物的每个金属原子周围的立体分子结构，与溶液中的配合物有关，我们主要测量了它们的XANES光谱，并使用DV-Xα分子轨道计算方法建立了光谱分析方法，并阐明了其结构和化学特征之间的关系。（n，n'，n“，n''' - 四甲基（2-氨基乙基）-1,4,8,11-111-tetraazacyCloteTradecane）的铜（ii）复合物形成晶体中的双核结构。如果Br^ - 是一种conterion andion这种复杂的形式是一个桥接的结构，并形成一个无关的结构，并且是一个符合clo__4^ime nive nive nive nive nif sonion a imim andion nion aniion a imion。在晶体和水溶液中，这种复合物的Xanes光谱在BR^的情况下分析了DV-Xα方法。水溶液中的络合物由Br^或氧原子（Clo_4^ - 阴离子中的一个氧原子）形成桥接结构。我们使用建议的模型结构通过DV-Xα计算方法分析了这些光谱，并阐明了它们之间的光谱变化。在固体样品的情况下，大约8340EV处的光谱变化显示了其堆叠结构中每个原子相互作用之间的差异，而对于吡啶溶液样品样品，复合物给出了唯一的结构，尽管堆叠结构在堆叠结构中略微偏离C轴。结果为复杂解决方案的红色起源提供了良好的信息。 [CUBR_2（CYCLAM）]和[Cu（Cyclam）（H_2O）_2] F_2-4H_2O是两种不同类型的Cyclam的络合物，1,4,8,11-tetraaza CycloteTradencane，以及这些配合物的固体和解决方案的XANES光谱与彼此不同。我们使用DV-Xα方法分析了光谱，结果表明，不同的光谱模式是通过在水溶液中与Cu（II）交换一个轴向Br^ - 在水溶液中的Cu（II）引起的，并且水溶液中的主要复合物是[Cubr（Cyclam）（cyclam）（H_2O）（H_2O）（H_2O）]^+。上提到的研究表明，通过我们的DV-Xα计算方法，XANES光谱分析是分析固体和溶液中原子间相互作用的非常有效的方法。较少的