Synthetic and Theoretical Studies of Silicon-Silicon Triple Bond Species

针对未知的硅硅三键（二硅氧烷）的电子过剩种类，我们研究了从硅基取代的双硅氧烷和双硅氧烷丙烯中还原消除乙烯和乙炔的方法。结果表明，硅基取代双硅环丙烷的合成是成功的。然而，用锂金属还原硅基取代的双硅环丙烷得到电子过剩的二硅氧烷的方法遇到了失败。在该项目的过程中，还发现苯基取代双硅环丙烷的热异构化产生了一种新的苯基取代1,4-二苯醚（Dewar-benzne）。此外，还尝试合成1,4-二苯金属配合物，但1,4-二苯与金属配合物的反应失败。在此基础上，提出了一种新的硅基取代1,4-二苯醚（杜瓦苯）的合成路线。最后，作为硅-芳香族化合物中电子过剩的第一个例子，1,4-二苯二氮通过锂金属还原（dewar -苯）成功分离。已有报道用AIM和ELF理论计算硅-硅、三键由于单键像孤对和反弯结构而显示出键序接近二的现象。分别用AIM和ELF计算程序对结果进行跟踪。这些理论方法被应用于另一个含硅化合物的键合问题

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