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

扩展超价m中心n电子键(MC-Ne：m[大于或等于]4)的研究才刚刚开始。在本项目中，对4c-6e和5c-6e进行了详细的研究。开始研究一种新型的扩展超价键，我们称之为MC^*-Ne(m=3和4)。虽然MC-Ne中的m个原子必须如定义的那样线性排列，但MC^*-Ne中的一个或多个原子不必线性排列。相反，m原子提供的轨道必须在相互作用的线性区域重叠。在1-(8-phz‘C&lt；10&gt；H_6)ZZ(C_&lt；10&gt；在硼氢化钠还原反应中，H_6Z‘Ph-8’)-1‘[1(Z，Z’)=(Se，S)，2(Z，Z‘)=(S，Se)，3(Z=Z’=Se)，4(Z=Z‘=S)]不受中心Z原子控制，而受外部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，为了更详细地研究这一领域，需要用简单的规则来确定基于核磁共振化学位移的几何和电子结构，这些结构是建立在理论上的，实验化学家们都很熟悉。根据分子轨道理论阐明了^&lt；77&gt；se核磁共振化学位移的来源：阐明了前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，这些相互作用在构建扩展的超价键中起着重要作用。对各种弱相互作用，如Z-Z，Z-Z=0，0=Z-Z=0进行了较好的分析，作为本项目的应用。

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.