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.

对扩展的高价值M-中心N电子键（MC-NE：M [大于或相等] 4）的研究仅仅是开始。在该项目中，详细研究了4C-6E和5C-6E。开始研究一种新型的扩展高价值键，我们称之为MC^*-NE（M = 3和4）。尽管MC-NE中的M原子必须按照定义的线性对齐，但MC^* - Ne中的一个或多个原子不需要线性对齐。取而代之的是，M原子提供的轨道必须在相互作用的线性区域重叠。所提出的IDE将解释包含主要组元素的有机化合物中的各种相互作用。Z-Z中央在1-（8-phz'c_ <10> h_6）中的Z-Z中心反应性在1-（8-phz'c_ <10> h_6）zz（C_ <10> H_6Z'PH-8'''''' - z-c_'6）中的反应性。（s，se），3（z = z'= se）和4（z = z'= s）]不受中央Z原子的控制，而是由硼氢钠降低钠的外部z'原子控制。这必须在不久的将来创造一个新的化学概念。我们意识到，基于NMR化学转移的几何和电子结构是必要的，基于NMR化学转移，该结构是基于理论建立并熟悉实验化学家的几何和电子结构，以便更详细地研究此类领域。根据MO理论阐明了 ^<77> se NMR化学位移的起源：针对PRE-α，α，β和γ效应，它们被阐明，以及对芳基群的定向效应。这些规则使我们能够分析和理解化合物的几何和电子结构。Quantum Chemical计算也被广泛应用于澄清弱相互作用，这些相互作用在构建扩展的高价值键中起着重要作用。各种弱相互作用，例如z --- z，z --- z = 0，和0 = z --- z = 0相互作用是我们项目的应用。