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

为了分析立体分子立体立体立体立体立体观点立体立体观点立体立体立体声立体声立体声立体声立体声立体声立体声立体声立体声立体声立体声在溶液中的平面金属复合物在溶液中的平面金属复合物在溶液中，我们主要使用Xanes分析方法测量了Xanes分析方法，光谱分析，光谱分析方法HOD并阐明了（II）-Tetrakis（2-氨基乙基）的关系（II） - 1,4,8,11 -TetraazacyClotetradecane）在晶体中形成了一个line木结构在溶液中讨论了络合物的行为，我们测量了在溶液和水溶液中的XANES光谱，并且在两个光谱之间使用了DV-Xαmetod。，水溶液中的复合物的Xanes光谱……更多的离子显示了与晶体中络合物的光谱的差异。在clo_4^-anion中）。同一光谱我们通过DV-Xα计算方法分析了这些光谱，提出的模型结构在固体的情况下触及的光谱变化。在吡啶样本中，将复合物块堆叠在另一个结构中，叠层结构中的Alltoot邻接分子与C轴略有偏差Cyclam，1,4,8,11-tetraaza环乙烷和固体中这些复合物的XANES，结果表明不同的光谱模式是由ANN H_2O交换的。水溶液中的Cu（II）分子是通过DV-Xα计算方法OW XANES光谱分析是非常有效的方法，可用于分析固体和溶液中的原子间相互作用