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Development of New Frontier Orbital Theory

新前沿轨道理论发展

基本信息

批准号：
11450328
负责人：
FUJIMOTO Hiroshi
金额：
$ 7.87万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

项目摘要

To control the selectivity in synthetic processes and to design novel reagents and catalysts, the basic theory in chemistry of general use, having high applicability and clarity is needed. In the old frontier orbital theory, a single orbital delocalized over the whole molecular framework is utilized to discuss the reactivity of molecules. As a result, it cannot provide us with reliable information when we deal with sizable systems. In this research, we have developed a new orbital interaction theory on the basis of the paired interaction orbital scheme and the projected reactive orbital method, explored by us. The new theory has been demonstrated to be extremely useful in clarifying the electronic mechanism of chemical reactions and in predicting the reactivity of molecules. The characteristics of a variety of chemical reactions can be represented in terms of amplitude and phase of interacting orbitals in each system. The hardness of the reaction site as a Lewis acid or a Lewis base ha … More s been formulated in terms of local electron-accepting or -donating ability and chemical hardness of the reaction site, and has been estimated numerically in molecular orbital calculations. The effects of substituent groups on the acid-base property in aminoboranes, and the factors that control the endo selectivity in the Diels-Alder reaction between cyclopropene and several substituted butadienes have been disclosed. It has been demonstrated that the concept of secondary orbital interactions that has been used frequently in literature for more than thirtyfive years lacks in a sound theoretical base. We have clarified next the electronic mechanism of activation of oxirane by biphenylenediol and the orbital interaction that brings an anomeric effect to saturated systems. The reaction paths of palladation of methylenecyclopropane and [3 + 2] addition to alkenes and of intramolecular rearrangements in ruthenium and iron dihydrides have been analyzed. The site selectivity in self-assembling of thiol monolayer on the gold surface has also been discussed by utilizing the theoretical method developed in this research. The effect of water as a solvent in chemical reactions has been studied by means of quantum chemical calculations, in collaboration with an experimental research group. Less

为了控制合成过程中的选择性，设计新的试剂和催化剂，需要通用的，具有高度适用性和清晰度的化学基础理论。在旧的前线轨道理论中，分子的反应性通常是用一个离域于整个分子骨架上的轨道来讨论的。因此，当我们处理大型系统时，它不能为我们提供可靠的信息。在本研究中，我们发展了一个新的轨道相互作用理论的基础上的配对相互作用轨道方案和投影反应轨道方法，我们探索。这一新理论在阐明化学反应的电子机制和预测分子的反应活性方面是非常有用的。各种化学反应的特征可以用每个系统中相互作用轨道的振幅和相位来表示。反应位点作为刘易斯酸或刘易斯碱的硬度关于我们的被制定在本地电子接受或捐赠能力和化学硬度的反应位点，并已在分子轨道计算数值估计。报道了取代基对氨基硼烷酸碱性的影响，以及环丙烯与几种取代丁二烯的Diels-Alder反应中，影响反应选择性的因素。结果表明，35年来文献中经常使用的次级轨道相互作用概念缺乏坚实的理论基础。接下来，我们阐明了联苯撑活化环氧乙烷的电子机制和给饱和体系带来异头效应的轨道相互作用。分析了亚甲基环丙烷的钯化反应和烯烃的[3 + 2]加成反应以及钌和铁的分子内重排反应的反应途径。本文还利用所建立的理论方法讨论了硫醇单分子膜在金表面自组装的位置选择性。与一个实验研究小组合作，通过量子化学计算研究了水作为溶剂在化学反应中的作用。少