Liquid Membrane Transport of Mercury Ion with Troponoid Dithiocrown Ethers and Their Theoretical Analysis

冠醚自从与各种金属离子形成配合物以来，在主客体化学中起着重要的作用。与此同时，为了实现与金属离子的选择性络合，新型离子载体的开发也受到了相当大的关注。另一方面，环α -二酮的邻苯二酮烯醇也与金属离子形成配合物。基于这些观察，我对具有对流层体单元的冠醚的主客体化学感兴趣，它有两个络合位点。然后，我合成了捕集Hg^<2+>的对流层蛋白二硫冠醚。到目前为止，用x射线晶体学测定了含HgCl_2的二硫冠醚的复杂结构，并用分子力学计算和半经验分子轨道计算（ANCHOR II）对其进行了估计。本研究对拟对流层二硫冠醚-汞配合物进行了半经验分子轨道计算（CAChe），并对假设分子“拟对流层冠醚”-锂配合物进行了从头算分子轨道计算。tropone的羰基在与金属离子的络合中起着重要的作用。

Crown ethers have playd an important role in host-guest chemistry since the discovery of the formation of their complexes with various metal ions. At the same time, considerable attention has been devoted to the development of new ionophores to achieve selective complexation with metal ions. On the other hand, tropolones enols of a cyclic alpha-diketone also form complexes with metal ions. Based on these observations, I was interested in the host-guest chemistry of the crown ethers with a troponoid unit, which have two complexing sites. Then, I have synthesized Hg^<2+> -capturing dithiocrown ethers of troponoids.So far, the complex structures of the dithiocrown ethers with HgCl_2 were determined by X-ray crystallography, and were estimated by molecular mechanics calculations and semi-empirical molecular orbital calculations (ANCHOR II).In this study, semi-empirical molecular orbital calculations (CAChe) of the troponoid dithiocrown ether-mercury complex have been carried out, and ab initio molecilar orbital calculations have been performed on hypothetical molecule "troponoid crown ether" -lithium complex.Carbonyl group of tropone plays an important role in the complexation with metal ion.