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Synthetic and Theoretical Studies of Silicon-Silicon Triple Bond Species

硅-硅三键物质的合成与理论研究

基本信息

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

项目摘要

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

对于未知的硅-硅三键(二硅炔)电子过剩物种，我们研究了硅基取代的双硅环丙烷和双硅环丙烯对乙烯和乙炔的还原消除。结果表明，硅基取代双硅环丙烷的合成是成功的。然而，硅基取代的双硅环丙烷与锂金属还原生成电子过剩物种二硅炔的反应失败了。在这个项目的过程中，还发现苯基取代的双硅环丙烷的热异构化得到了一个新的苯基取代的1，4-二硅烷(杜瓦苯)作为副产物。此外，1，4-二硅苯金属络合物的合成尝试也以失败告终。通过这些研究，揭示了一条新的硅基取代1，4-二硅(杜瓦苯)的合成路线。最后，作为第一个硅芳烃电子过剩物种的例子，1，4-二硅苯二烯被成功地通过1，4-二(杜瓦苯)的锂金属还原而分离出来。这一结果的手稿目前正在准备中。据报道，AIM和ELF理论计算的硅-硅三键显示出近两个键级，这是因为一个键类似单键对和反式弯曲结构。我们分别使用AIM和ELF计算程序跟踪他们的结果。将这些理论方法应用于含硅化合物的另一个成键问题。