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Construction of Compound System with Extended Hypervalent Bonds Utilizing Naphthalene and Anthracene Frameworks

利用萘和蒽骨架构建具有扩展高价键的化合物体系

基本信息

批准号：
16550038
负责人：
HAYASHI Satoko
金额：
$ 2.24万
依托单位：
Wakayama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550038/
关键词：
extended hypervalent bond nature of bond theoretical calculation naphthalene anthracene main group elements lone pair linear bonds 拡張超原子結合価系 mc-ne 同核カルコゲン異核カルコゲン量子化学計算

项目摘要

Investigations on extended hypervalent m-center n-electron bonds (mc-ne : m 【greater than or equal】 4) are just the beginning. In this project, 4c-6e and 5c-6e are investigated in detail. A new type of extended hypervalent bonds are started to investigate, which we call mc^*-ne (m = 3 and 4). While m atoms in mc-ne must align linearly, as defined, one or more atoms in mc^*-ne need not to align linearly. Instead, orbitals supplied by the m-atoms must overlap in the linear area of the interactions. The proposed ides will explain various interactions in organic compounds containing main group elements.The reactivity of central Z-Z in the extended hypervalent Z'---Z-Z---Z' 4c-6e in 1-(8-PhZ'C_<10>H_6)ZZ(C_<10>H_6Z'Ph-8')-1' [1 (Z, Z') = (Se, S), 2 (Z, Z') = (S, Se), 3 (Z = Z' = Se), and 4 (Z = Z' = S)] is not controlled by the central Z atoms but by the outside Z' atoms, in the sodium boro-hydride reduction. This must create a new concept of chemistry in near future.We realize that plain rules are necessary to determine geometric and electronic structures based on the NMR chemical shifts, which are founded in theory and are familiar to experimental chemists, to study such field in more detail. Origin of ^<77>Se NMR chemical shifts are elucidated based on the MO theory : They are clarified for pre-α, α, β, and γ effects, together with the orientational effect on aryl groups. The rules enable us to analyze and understand the geometrical and electronic structures of the compounds.Quantum chemical calculations are also widely applied to clarify weak interactions, which play an important role in the construction of extended hypervalent bonds. Various weak interactions such as Z---Z, Z---Z=0, and 0=Z---Z=0 interactions are well analyzes, as the applications of our project.

对扩展的超价m-中心n-电子键（mc-ne：m [大于或等于] 4）的研究仅仅是开始。在本项目中，4c-6 e和5c-6 e被详细研究。我们开始研究一类新的扩展超价键，称之为mc^*-ne（m = 3和4）。虽然mc-ne中的m个原子必须按照定义线性排列，但mc^*-ne中的一个或多个原子不需要线性排列。相反，m原子提供的轨道必须在相互作用的线性区域重叠。研究了1-（8-PhZ ′ C_<10>H_6）ZZ（C_ H_6Z <10>′ Ph-8 ′）-1 ′ [1（Z，Z ′）=（Se，S），2（Z，Z ′）=（S，Se），3（Z，Z ′）=（S，Se）]中扩展超价Z ′-Z-Z--Z ′ 4c-6 e中心Z-Z的反应活性（Z = Z' = Se）和4（Z = Z' = S）]不受中心Z原子的控制，而受外部Z'原子的控制。我们认识到，为了更深入地研究这一领域，需要根据实验化学家熟悉的、有理论基础的NMR化学位移确定几何结构和电子结构的简单规则。根据<77>分子轨道理论，阐明了~ 13 Se NMR化学位移的起因：前α、α、β和γ效应，以及芳基的取向效应。这些规则使我们能够分析和理解化合物的几何结构和电子结构，量子化学计算也被广泛应用于阐明弱相互作用，这在构建扩展超价键中起着重要作用。作为本课题的应用，我们对各种弱相互作用如Z-Z、Z-Z=0和0=Z-Z=0相互作用进行了较好的分析。