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A Study on the structure and reactivity of encounter complex

遭遇复合体的结构和反应性研究

基本信息

批准号：
16205009
负责人：
KAIZU Youkoh
金额：
$ 25.63万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16205009/
关键词：
encounter complex reaction of photo-excitation energy-transfer mixed-ligand complex ruthenium(II) and chromium(III) complexes aqueous solution and mixed-solvent ethanol and acetonitrile congeniality between ligands bipyridine and phenanthrol

项目摘要

It has been thought that the tris-chelate metal-complexes of mixed-ligands of some poly-pyridines are completely spherical in chemical reaction in solution. However, the experimental results of energy-transfer rate-constant from the mixed-ligand Ru(II)-complex to Cr(III) complex indicate that the energy-acceptor complexes do not exist around the mixed-ligands complexes of energy-donor in encounter complex in aqueous solution. In other words, the relative geometry between the mixed-ligand Ru(II)-complex and Cr(III) complex are not isotropic but anisotropic even in encounter complex in solution. The congeniality between donor's ligand and acceptor's ligand is very important for the structure of encounter complex in aqueous solution, for example, hydrophobicity and hydrophilicity.In mixed-solvents of water : ethanol and water : acetonitrile (v.v. 8 : 2 and 6 : 4), the relative geometry of encounter complex is different from that in aqueous solution. These results indicate that the solvent molecules of ethanol and acetonitrile affect on the relative geometry of encounter complex.Therefore, the determination of the rate-constant of photo-excitaion energy-transfer between metal-complexes makes it possible for the structure of encounter complex in solution as molecular level.The results in this work have a very wide application, especially in the region of chemical reaction in a living body.

某些聚吡啶混合配体的三螯合金属配合物在溶液中的化学反应被认为是完全球形的。然而，从混合配体Ru（II）配合物到Cr（III）配合物的能量转移速率常数的实验结果表明，水溶液中能量给体遭遇配合物的混合配体配合物周围不存在能量受体配合物。换句话说，混合配体Ru（II）配合物和Cr（III）配合物之间的相对几何形状不是各向同性的，而是各向异性的，即使在溶液中遇到配合物。水溶液中给体配体与受体配体的相合性对配合物的疏水性和亲水性等结构有重要影响，在水：乙醇和水：乙腈（体积比为8：2和6：4）混合溶剂中，配合物的相对几何构型与水溶液中不同。这些结果表明，溶剂分子乙醇和乙腈影响了配合物的相对几何构型，因此，确定了金属配合物间光激发能量转移的速率常数，为从分子水平上研究溶液中配合物的结构提供了可能，这一结果在生物体内化学反应领域有着广泛的应用。