Cationic Clusters Consisting of Heavier Group 14 Elements

由较重的第 14 族元素组成的阳离子簇

• 批准号: 14078204
• 负责人: SEKIGUCHI Akira
• 金额: $ 16.38万
• 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 on Priority Areas
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078204/
• 关键词: Element Chemistry; Heavier Group 14 Element; Cluster; Cation; Radical; Aromaticity; Silicon; Functional materials; 高周期14族元素; 高周期14族元素多重結合; 高周期14族元素芳香族化合物; 高周期14族元素カチオン種; 高周期14族元素アニオン種; 高周期14族元素ラジカル種; 高周期14族元素多重結合化合物; 不飽和小員環化合物; 有機ゲルマニウム化合物

The chemistry of the stable ionic species of heavier group 14 elements has been studied, including both cationic and anionic species together with radical species. The electronic and crystal structural features of these ionic species, both in the solid state and in solution, have been investigated by the experimental and computational study.1. The highly crowded 3,3-bis(di-tert-butylmethylsily1)-1,2-bis(tri-tert-butylsilyl)cyclotrisilene, an unsaturated three-membered compound with an Si=Si bond, was treated with triphenylmethylium tetraarylborate to produce (di-tert-butylmethylsilyl)bis(tri-tert-butylsilyl)cyclotrisilenylium ion, representing the first isolable silicon congener of the cyclopropenylium ion. The X-ray crystal structure and spectral data show that the cyclotrisilenylium ion is not only a free silyl cation but also a 2a electron aromatic species with delocalization of the positive charge over the three-membered skeleton.2. The heavy cyclobutadiene dianions, tetrakis(di-tert-butylmethylsily1)-1,2-disila-3,4-digermacyclobutadiene dianion and tetrakis(di-tert-butylmethylsilyl)tetrasilacyclobutadiene dianion, have been synthesized by the reductive dehalogenation of the corresponding precursors with potassium graphite. The cyclobutadiene dianions were found to be nonaromatic by their structural features and the lack of diatropic ring current effects.3. 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(methypsilyl]sily1 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 a-character of both radicals, corresponding to a planar geometry and sp2 hybridization of the radical centers.

研究了重14族元素的稳定离子物种的化学，包括阳离子和阴离子物种以及自由基物种。通过实验和计算研究了这些离子物种在固态和溶液中的电子和晶体结构特征.高度拥挤的3，3-双（二叔丁基甲基硅烷基）-1，2-双（三叔丁基硅烷基）环三硅烯是一种具有Si=Si键的不饱和三元化合物，用三苯基甲基四芳基硼酸盐处理，生成（二叔丁基甲基硅烷基）双（三叔丁基硅烷基）环三硅烯鎓离子，代表环丙烯鎓离子的第一个可分离的硅同系物。X-射线晶体结构和光谱数据表明，环三硅烯鎓离子不仅是一个游离的硅阳离子，而且是一个带正电荷的离域2a电子芳香物种.用钾石墨还原脱卤法合成了重环丁二烯二价阴离子四（二叔丁基甲基硅基）-1，2-二硅杂-3，4-二锗环丁二烯二价阴离子和四（二叔丁基甲基硅基）四硅杂环丁二烯二价阴离子。根据环丁二烯二价阴离子的结构特征和环向阻流效应的缺乏，确定其为非芳香型.三[二叔丁基（甲基）硅基]甲硅烷基和甲锗烷基阴离子与二氯锗撑二氧六环配合物发生单电子氧化反应，生成稳定的三[二叔丁基（甲基）硅基]甲硅烷基和甲锗烷基自由基。甲硅烷基和甲锗烷基自由基的晶体结构都显示出围绕自由基中心的完全平面几何结构。EPR谱表明这两个自由基的a-字符，对应于一个平面的几何形状和sp2杂化的自由基中心。

项目成果

Sekiguchi, Tetrasilacyclobutadiene ('Bu2MeSi)4Si4 : A New Ligand for Transition Metal Complexes.

Sekiguchi，四硅环丁二烯 (Bu2MeSi)4Si4：过渡金属配合物的新配体。

• 发表时间: 2005
• 期刊: Journal of the American Chemical Society 127
• 作者: K.Takanashi;V.Ya.Lee;T.Matsuno;M.Ichinohe;A.
• 通讯作者: A.

A Chemical Trick : How to Make a Digermane from a Disilene, Formation of Δ^3-1,2,3,4-Disiladigermetene

化学技巧：如何从二硅烯制备二硅烯，形成 Δ^3-1,2,3,4-二硅二硅烯

• 发表时间: 2003
• 期刊: Journal of the American Chemical Society 125・20
• 作者: Vladimir Ya.Lee

The First Isolable 1,1-Dilithiogermane and its Unusual Dimeric Structure - a New Effective Reagent for the Preparation of Doubly-Bonded Derivatives of Group 14 Elements

第一个可分离的1,1-二锂锗烷及其独特的二聚结构——一种用于制备14族元素双键衍生物的新型有效试剂

• 发表时间: 2002
• 期刊: Angewandte Chemie, International Edition 41・9
• 作者: M.Ichinohe;M.Toyoshima;R.Kinjo;A.Sekiguchi;Akira Sekiguchi;Tsukasa Matsuo;M.Kira;中條善樹他;Akira Sekiguchi
• 通讯作者: Akira Sekiguchi

Akira Sekiguchi: "Tetrahedranyllithium : Synthesis, Characterization, and Reactivity"Journal of the American Chemical Society. 125・42. 12684-12685 (2003)

Akira Sekiguchi：“四面体锂：合成、表征和反应性”美国化学会杂志 125・42（2003 年）。

Cyclobutadiene Dianion (Award Accounts)

环丁二烯 Dianion（奖励账户）

• 发表时间: 2004
• 期刊: Bulletin of the Chemical Society of Japan 77・2
• 作者: Hiroyuki Miyake;Hiroshi Tsukube;A.Sekiguchi 他1名;T.Watanabe 他2名;T.Matsuo 他1名;F.Akagi 他2名;H.Kawaguchi 他1名;T.Matsuo 他1名;T.Matsuo 他1名
• 通讯作者: T.Matsuo 他1名