Synthesis, Structure, and Reactivity of Heavier Group 14 Element-centered Free Radicals : From Phantom Species to Grams-Order-Scale Materials

以较重第 14 族元素为中心的自由基的合成、结构和反应性：从幽灵物种到克级材料

• 批准号: 16205008
• 负责人: SEKIGUCHI Akira
• 金额: $ 32.61万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 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-16205008/
• 关键词: Element Chemistry; Heavier Group 14 Element; Main Group Element; Free Radical; Spin Chemistry; Cation; Anion; Oxidation and Reduction; 電子移動反応; 電子状態; 高周期元素; ジシレン; ジシレンジアニオン; 金属置換シリルラジカル; シリレンアニオンラジカル; 高周期14族元素; 高周期14族元素多重結合; 高周期14族元素ラジカル種

The chemistry of the stable free radicals of heavier group 14 elements has been studied, including both neutral and charged radical species. The electronic and crystal structural features of these radicals, both in the solid state and in solution, are compared with each other. The most important parameters affecting the stability, geometry and electronic configuration of the radicals are investigated, based upon the experimental and computational data.1. Upon one-electron reduction with ^tBuLi, tetrakis(di-tert-butylmethylsilyl)disilene produced a disilene anion radical, which was isolated in the form of its lithium salt. The molecular structure was established by X-ray crystallography, which showed a nearly orthogonal structure with the central Si-Si bond length of 2.341(5) Å. One of the central Si atoms has radical character, whereas the other Si atom has silyl anion character. The EPR study indicates that rapid spin exchange occurs between these central Si atoms on the EPR time scale.2. The one-electron oxidation reaction of tris[di-tert-butyl(methyl)silyl]silyl and germyl anions with dichlorogermylene dioxane complex resulted in the formation of stable tris[di-tert-butyl(methyl)silyl]silyl and germyl radicals. The crystal structures of both silyl and germyl radicals showed a completely planar geometry around the radical centers. The EPR spectra indicate the p-character of both radicals, corresponding to a planar geometry and sp^2 hybridization of the radical centers.3. The one-electron reduction of tris[di-tert-butyl(methyl)silyl]aluminum and-gallium with alkali metals (Li, Na, K) resulted in the formation of the corresponding radical anions [(tBu_2MeSi)_3Al]^-・and [(^tBu_2MeSi)_3Ga]・^-. Their molecular structures were established by X-ray crystallography, which showed a nearly planar geometry around the radical centers.

项目成果

The Isolable Anion Radical of Blue Disilene (^tBu_2MeSi)_2,Si=Si(SiMe^tBu_2)_2 Formed upon One Electron Reduction : Synthesis and Characterization

一个电子还原形成的蓝色二硅烯 (^tBu_2MeSi)_2,Si=Si(SiMe^tBu_2)_2 的可分离阴离子自由基：合成与表征

• 发表时间: 2004
• 期刊: Journal of the American Chemical Society 126・31
• 作者: T.;Iihoshi;T.;Sato;N.;Matsumoto;Akira Sekiguchi
• 通讯作者: Akira Sekiguchi

Tetrasilatetrahedranide: The First Silicon Cage Anion

四硅四面体：第一个硅笼阴离子

• 发表时间: 2004
• 期刊: Angewandte Chemie, International Edition 43・48
• 作者: Y. Niwa;et. al.;Vladimir Ya.Lee
• 通讯作者: Vladimir Ya.Lee

An Isolable Disilyne Anion Radical and a New Route to the Dislienide Ion upon Reduction of a Disilyne

可分离的二甲硅烷阴离子自由基和二甲硅烷还原后生成二甲醚离子的新途径

• 发表时间: 2007
• 期刊: Journal of the American Chemical Society 129・1
• 作者: Oki;Keisuke ; Otsuka;Takuhiro ; Kaizu;Youkoh;Rei Kinjo
• 通讯作者: Rei Kinjo

Unexpected Hydrolithiation of the M=M' Double Bond (M, M' Si. Ge) with BuLi

M=M 双键 (M, M Si.Ge) 与 BuLi 的意外氢化锂化

• 发表时间: 2004
• 期刊: Chemistry Letters 33・2
• 作者: M.Ichinohe;K.Sanuki;S.Inoue;A.Sekiguchi;Masaaki Nakamoto;Vladimir Ya.Lee;Masaaki Nakamoto;Tsukasa Matsuo;Vladimir Ya. Lee
• 通讯作者: Vladimir Ya. Lee

Photochemical Generation of Halo(silyl)silylene : Spectroscopic Observation and Reactivity

• DOI: 10.1246/cl.2004.1420
• 发表时间: 2004-10
• 期刊: Chemistry Letters
• 影响因子: 1.6
• 作者: Takashi Tanaka;M. Ichinohe;A. Sekiguchi