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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配合物各金属原子周围的立体分子结构与配合物性质的关系，我们主要对其进行了XANES光谱测量，采用DV-Xα分子轨道计算方法建立了光谱分析方法，阐明了其结构与化学性质之间的关系。铜（II）配合物（N，N‘， N’， N' -四（2-氨基乙基）-1,4,8,11-四氮杂环十四烷）在晶体中形成双核结构。如果Br^-是一个反阴离子，这个络合物形成一个桥式结构，如果ClO_4^-是一个反阴离子，这个络合物形成一个非桥式结构。为了讨论配合物在溶液中的行为，我们测量了该配合物在晶体和水溶液中的XANES光谱，并用DV-Xα法对光谱进行了分析。在Br^-桥接配合物的情况下，两个光谱之间没有变化。而对于未桥接的配合物，水溶液中的XANES光谱与晶体中的XANES光谱有明显的差异。两个光谱的DV-Xα计算表明，水溶液中的配合物由Br^-或氧原子（一个氧原子在ClO_4^-阴离子上）形成桥接结构。双（1,2-二酮二zimato）镍（II）配合物形成两种不同类型的一维堆叠结构。配合物的晶体样品给出了两种不同类型的XANES光谱，而它们的吡啶溶液样品只有相同的光谱。利用所提出的模型结构，用DV-Xα计算方法对这些光谱进行了分析，明确了它们之间的光谱变化。在固体样品中，在8340eV左右的光谱变化表明了每个原子相互作用在其堆叠结构上的差异，而在吡啶溶液样品中，配合物给出了唯一的一种结构，即复杂分子一个叠在另一个上面，尽管堆叠结构中的相邻分子稍微偏离c轴。该结果为复解红色的来源提供了很好的信息。[CuBr_2(cyclam)]和[Cu(cyclam)(H_2O)_2]F_2-4H_2O是环十四烷、1,4,8,11-四氮环十四烷的两种不同类型配合物，它们在固溶中的XANES光谱不同。用DV-Xα方法分析了光谱，结果表明，不同的光谱模式是由水溶液中含有H_2O分子的单轴Br^-与Cu（II）交换引起的，水溶液中的主要配合物是[CuBr(cyclam)(H_2O)]^+。上述研究表明，用DV-Xα计算方法进行XANES光谱分析是分析固体和溶液中原子间立体相互作用的有效方法。少