Synthetic and Theoretical Studies of Silicon-Silicon Triple Bond Species

硅-硅三键物质的合成与理论研究

• 批准号: 13640523
• 负责人: KABE Yoshio
• 金额: $ 2.05万
• 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 (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640523/
• 关键词: silicon-silicon triple bond; disilyne; bissilacyclopropane; bissilacrclopropenyl; 1,4-disila(Dewar-benzene); AIM calculation; ELF calculation; ジシラデュワ-ベンゼン; ビスシラシクロプロペン; ジシラデュワーベンゼン; 理論計算

Toward electron excess species of unknown silicon-silicon triple bond (disilyne), we investigated the reductive elimination of ethylene and acetylenes from silyl-substituted bissilacyclopropane and bissilacyclopropenyl. As a-result, the synthesis of silyl-substituted bissilacyclopropane was successful. However, the Li-metal reduction of silyl-substituted bissilacyclopropane with Li-metal to give an electron excess species of disilyne met with failure. On the way of this project, it was also found that the thermal isomerization of phenyl-substituted bissilacyclopropane afforded a new phenyl-substituted 1,4-disila(Dewar-benzne) as a byproduct. Furthermore synthetic attempt a 1,4-disilabenzene metal complexesthe reaction of 1,4-disila(Dewar-benzene) with metal complexes were failed. From these studies, a new synthetic route for silyl-substituted 1,4-disila(Dewar-benzene) was disclosed. Finally, as a first example of electron excess species of silicon-aromatic compounds, 1,4-disilabenzene diaion was successfully isolated by the Li-metal reduction of 1,4-disia(Dewar-benzene). The manuscript of this result is now in preparationIt have been reported that AIM and ELF theoretical calculation of silicon-silicon, triple bond showed bond order nearly two because of one bond like alone-pair and the trans-bent structures. We followed their results using AIM and ELF calculation program respectively. These theoretical methods were applied to another bonding problem of silicon-containing compounds

朝着未知硅三键（DISILENE）的电子过量物种，我们研究了从甲硅烷基建立的二甲硅烷基丙烷丙烷和二甲丙基苯基中的乙烯和乙酰基的还原性消除。作为A-反应，甲硅烷基取代的二甲丙烷丙烷的合成成功。然而，用李 - 金属的li-metal降低了甲硅烷基取代的二甲丙烷丙烷，使电子过量的disilyne物种遇到了失败。在该项目的途中，还发现苯基取代的二硅烷丙烷的热异构化提供了一种新的苯基取代的1,4-二硅（Dewar-benzne）作为副产品。此外，合成尝试使1,4-二甲硅（Dewar-苯苯）与金属配合物的1,4-二甲苯苯金属复合物反应失败了。从这些研究中，揭示了一项新的甲硅烷基取代的合成途径（杜瓦 - 苯苯）。最后，作为硅芳族化合物的电子过量物种的第一个例子，通过1,4-二氨基（Dewar-benzene）的Li-i-Metal还原成功地分离了1,4-二甲苯二乙烯。现在已经有报道说，该结果的手稿已经在准备中，硅 - 硅硅的目标和精灵理论计算，三键显示键顺序，几乎是两个键，因为一个键，如单独的对和透射结构。我们分别使用AIM和ELF计算计划遵循他们的结果。这些理论方法应用于含硅化合物的另一个键合问题

项目成果

Y.Ishida, A.Sekiguchi, Y.Kabe: "1,4,5-Trigermabicyclo[2.1.0]pent-2-en-5-ylium : The Isolabe Bishompcyclopropenylium Ion Containing a Heavier Group 14 Element"J.Am.Chem.Soc.. 125. 11468-11469 (2003)

Y.Ishida、A.Sekiguchi、Y.Kabe：“1,4,5-Trigermabicyclo[2.1.0]pent-2-en-5-ylium：含有较重 14 族元素的 Isolabe Bishompcyclopropenylium 离子”J.Am.

Y.Kabe, H.Ohgaki, T.Yamagaki, H.Nakanishi, W.Ando: "The Photochemical Reaction of 1,2-digermacyclobutane with C60 : Possible Example of closed [6,5]-bridged fullerene Derivatives of Germacyclopropane"J.Organomet.Chem.. 636. 82-90 (2001)

Y.Kabe、H.Ohgaki、T.Yamagaki、H.Nakanishi、W.Ando：“1,2-二germacyclobutane与C60的光化学反应：Germacyclopropane的闭合[6,5]-桥接富勒烯衍生物的可能示例”J

N.Fukaya, M.Ichinohe, Y.Kabe, A.Sekiguchi: "Ring Contraction of 1,2-Digermacyclohexa-1,4-diene to (Germacyclopenta-3-enyl)germylene"Organometallics. 20. 3364-3366 (2001)

N.Fukaya、M.Ichinohe、Y.Kabe、A.Sekiguchi：“1,2-Digermacyclohexa-1,4-diene 到 (Germacyclopenta-3-enyl)germene 的环收缩”有机金属化合物。