权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Synthesis of Novel Silicon-containing Multiple-bond Compounds by Taking Advantage of Steric Protection and Investigation of Their Structures and Reactivities

利用空间保护合成新型含硅多重键化合物及其结构和反应性研究

基本信息

批准号：
07454193
负责人：
TOKITOH Norihiro
金额：
$ 5.12万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

项目摘要

1.The first stable silanethione Tbt(Tip)Si=S(1 : Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Tip=2,4,6-triisopropylphenyl)was successfully synthesized by the desulfurization of the corres-ponding tetrathiasilolane, Tbt(Tip)SiS_4, with triphenylphoshine in hexane. Silanethione 1 was isolated as stable yellow crystals and it showed a characteristic downfield shifted signal at+166.6ppm(in C_6D_6)in the ^<29>Si NMR spectra suggesting the sp^2 character of the central silicon. The X-ray crystallographic structural analysis revealed that the Si-S bond length of 1 is ca. 9% shorter than that of the typical Si-Si single bond compounds and the silathiocarbonyl unit of 1 has a completely trigonal planar geometry as in the case of ketones. Silinethione 1 was found to have an enough space around the central siliconatom to react with small molecules, though the bulky substituents on Si atom of 1 effectively prevent its self-dimerization.2.The synthesis of a stable silaketeneimine, Tbt(Mes)Si=C … More =NAr, was also examined by the reaction of a sterically protected silylene Tbt(Mes)Si : (Mes=mesityl), which was found to be readily available on the thermolysis of the corresponding disilenes Tbt(Mes)Si=Si(Mes)Tbt, with several kinds of isocyanides bearing bulky aromatic substituents. The spectroscopic investigation on the resulting blue or greenish blue pastes revealed that the silylene adducts of isocyanides here obtianed were not the cumulative double-bond species but the novel silylene-isocyanide complexes. This is the first examples of isolated silyene-Lewis base complexes.3.The thermal reaction of an overcrowded silascylopropane derivative in the presence of elemental selenium resulted in the formation of silaneselone Tbt(Dip)Si=Se(Dip=2,6-diisopropyl-phenyl)stable in solution.As an extension of this research project, the double-bond species between germanium and heavier chalcogen atoms kinetically stablilized by taking advantage of the Tbt group, i.e.germanethiones, germaneselones, and germanetellones Tbt(R)Ge=X[X=S,Se, Te ; R=Tip or CH(SiMe_3)_2], were all synthesized and isolated as stable crystalline compounds. These results have been partially published as papers listed in the references. Less

1.用三苯基膦酸在己烷中脱硫，成功合成了第一个稳定的硅硫酮Tbt(Tip)Si=S（1: Tbt=2,4,6-三[二（三甲基硅基）甲基]苯基，Tip=2,4,6-三异丙基苯基）。硅烷硫酮1为稳定的黄色晶体，在^<29>Si核磁共振光谱中，在+166.6ppm（在C_6D_6中）表现出特征性的下移信号，表明中心硅具有sp^2特征。x射线晶体结构分析表明，1的Si-S键长度比典型的Si-Si单键化合物短约9%，1的硅硫代羰基单元与酮类化合物一样具有完全的三角形平面几何结构。发现硅硫酮1的中心硅原子周围有足够的空间与小分子反应，尽管硅原子1上庞大的取代基有效地阻止了它的自二聚化。用具有空间保护作用的硅烯Tbt(Mes)Si: （Mes=mesityl）反应制备了稳定的硅烯甲亚胺Tbt(Mes)Si=C…More =NAr，该反应发现，相应的二硅烯Tbt(Mes)Si=Si(Mes)Tbt与几种带有大体积芳香取代基的异氰化物可以很容易地进行热裂解。对所制得的蓝色或青蓝色糊状物的光谱研究表明，所制得的异氰化物硅烯加合物不是累积双键，而是新型的硅烯-异氰化物配合物。这是分离的硅烷-路易斯碱配合物的第一个例子。在单质硒的存在下，对一个过度拥挤的硅环丙烷衍生物进行热反应，生成了在溶液中稳定的硅烷酮Tbt(Dip)Si=Se（Dip=2,6-二异丙基苯基）。作为本研究项目的延伸，利用Tbt基团，即germanethiones， germaneselones, germanetellones, Tbt(R)Ge=X[X=S,Se, Te；R=Tip或CH(SiMe_3)_2]，均为稳定的晶体化合物。这些结果已部分作为论文发表在参考文献中。少