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.第一个稳定的硅烷硫酮TBT（尖端）Si = S（1：TBT = 2,4,6-Tris [Bis（三甲基甲硅烷基）甲基]苯基，TIP = 2,4,6-三异丙苯基苯基苯基苯基苯基苯基苯基苯基苯基甲基甲基苯基甲基苯甲酸的尖端（均由corres-pond）ialsialolane tortathialsialolane thiasilolane tbtt（己烷中的triphenylphine。硅烷硫酸1分离为稳定的黄色晶体，在 ^<29> si nmr光谱中，它显示出一个特征性的下场偏移信号（在C_6D_6中），表明中央硅的SP ^2特征。 X射线晶体结构分析表明，Si-S键长为1。与典型的Si-Si单键化合物的短9％和1的Silathiocarbonyl单元具有完全三角平面的几何形状，如酮而言。 Silinethione 1 was found to have an enough space around the central siliconatom to react with small molecules, though the bulky subtituents 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），发现在相应的dialenes tbt（MES）Si = Si（MES）TBT的热解时很容易获得，其中几种具有光谱调查的异氰酸酯，这些异氰化物对所产生的蓝色或绿色的蓝色的新型浓度均可添加液体果元素，这些异型是无元素的浓度，是浓度的浓度，是荷兰的液体固定的液体果元素。 3.在存在元素硒的情况下，过度拥挤的硅烷 - 丙烷衍生物的热反应形成了硅烷酮TBT（DIP）SI = SE = Se = Se = Se = se（DIP = 2,6-二甲基苯基 - 苯基苯基稳定）在溶液中稳定的稳定物种，这是在溶液中的繁殖物。通过利用TBT组，即Germanethiones，Germaneselones和Germanetellones TBT（R）GE = X [X = S，SE，TE，TE; r = tip或ch（sime_3）_2]，全部合成并隔离为稳定的晶体化合物。这些结果已部分发表，作为参考文献中列出的论文。较少的