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.

较重的第 14 族元素的稳定离子种类的化学性质已得到研究，包括阳离子和阴离子种类以及自由基种类。通过实验和计算研究，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。1．高度拥挤的3,3-双(二叔丁基甲基甲硅烷基1)-1,2-双(三叔丁基甲硅烷基)环三硅烯是一种带有Si=Si键的不饱和三元化合物，用四芳基硼酸三苯基甲基鎓处理生成(二叔丁基甲基甲硅烷基)双(三叔丁基甲硅烷基)环三甲硅烷基鎓离子，代表第一个可分离的硅同系物环丙烯鎓离子。 X射线晶体结构和光谱数据表明，环三硅鎓离子不仅是游离的硅基阳离子，而且是正电荷在三元骨架上离域的2a电子芳香族物种。 2．通过相应前体的还原脱卤合成了重环丁二烯二价阴离子，四(二叔丁基甲基硅基1)-1,2-二硅基-3,4-二甲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钾石墨。由于环丁二烯二价阴离子的结构特征和缺乏环流效应，环丁二烯二价阴离子属于非芳香族。 3．三[二叔丁基(甲基)甲硅烷基]甲硅烷基和甲芽基阴离子与二氯甲锗烷二恶烷络合物发生单电子氧化反应，形成稳定的三[二叔丁基(甲基)甲硅烷基]甲硅烷基和甲芽基自由基。甲硅烷基和甲锗烷基的结构在自由基中心周围显示出完全平面的几何形状，EPR光谱表明这两个自由基的α特征，对应于平面几何形状。和自由基中心的sp2杂化。

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.

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）。

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

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