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ESR Studies of Charge Effect on the Structure of Radical Ions,distorted by Jahn-Teller Effect

电荷效应对杨-特勒效应扭曲的自由基离子结构的 ESR 研究

基本信息

批准号：
61470012
负责人：
HASEGAWA Akinori
金额：
$ 4.48万
依托单位：
Kogakkan University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1986
资助国家：
日本
起止时间：
1986 至 1988
项目状态：
已结题

项目摘要

We have already revealed that tetramethyl silane (TMS) is the most effective matrix to produce and stabilize rabical anions, and reported a series of radical anions which have structures distorted by Jahn-Teller effect. In the other hand, freon was shown to be one of effective and convenient matrices for radical cations, which often undergo Jahn-Teller distortion. Stannane, SnH_4, is the only one example that both of radical anion and radical cation were produced from mother molecules in these matrices.The aim of this project is to detect radical anion and radical cation derived from the same origin and compare their distorted structures. However, there has recently been an upsurge of interest in radical cations so that several studies on radical cations were performed independently. Theoretical calculations were carried out for substituted benzene cations and their structures distorted by Jahn-teller effect were determined. A distorted ring structure was revealed for the tetramethylcyclobutadiene radical cataion which was obtained by annealing of dimethylacetylene radical cation. Two types of ring structures were suggested for halogenoalkane radical cations. As for radical cations of dialkyl mercury derivatives, their distorted structures were compared with those obtained for alkane cations.On the other hand, exposure of metal complex containing platinum metal in solvents resulted in by electron addition to give anion, followed by protonation, to give proton addact. Their structures were discussed.Moreover, both of radical cation and radical anion were yielded from yellow phosphorus, P_4, which has a tetrahedral structure, in solid matrices. Detailed analysis is under way. However, drastic difference in the distorted structure was suggested between the radical cation and the radical anion.

我们已经揭示了四甲基硅烷（TMS）是产生和稳定自由基阴离子的最有效基质，并报道了一系列因Jahn-Teller效应而结构扭曲的自由基阴离子。另一方面，氟利昂被证明是自由基阳离子的有效且方便的基质之一，自由基阳离子经常发生杨-泰勒畸变。锡烷（SnH_4）是唯一一个自由基阴离子和自由基阳离子均由这些基质中的母分子产生的例子。该项目的目的是检测来自同一来源的自由基阴离子和自由基阳离子并比较它们的扭曲结构。然而，最近人们对自由基阳离子的兴趣高涨，因此对自由基阳离子的几项研究都是独立进行的。对取代苯阳离子进行了理论计算，并确定了因 Jahn-teller 效应而扭曲的结构。通过二甲基乙炔自由基阳离子退火获得的四甲基环丁二烯自由基阳离子揭示了扭曲的环结构。对于卤代烷自由基阳离子，提出了两种类型的环结构。对于二烷基汞衍生物的自由基阳离子，将其扭曲结构与烷烃阳离子的结构进行了比较。另一方面，将含有铂金属的金属配合物暴露在溶剂中，导致电子加成产生阴离子，然后质子化，得到质子加合物。并对它们的结构进行了讨论。此外，固体基质中具有四面体结构的黄磷P_4产生了自由基阳离子和自由基阴离子。详细分析正在进行中。然而，自由基阳离子和自由基阴离子之间的扭曲结构存在巨大差异。