Syntheses and Properties of Novel Organic Compounds of Heavier 14,15, and 16 Group Elements

在本研究中进行了以下三个项目。(1)稳定硅离子的合成及其反应活性。(2)五配位草甘膦和草甘膦的合成及其反应活性。(3) 14族和16族元素间双键化合物的合成及其反应性。(1)用（ArX）_3SiCl与AgClo_4反应，Mes_3 SiCl与SbCl_5反应，合成了硅离子（ArX）_3Si^+（X=S, Se; Ar=2,4,6-三叔丁基苯基）和mes_3Si^+。这两种反应的产物都可以用硅离子作为中间体来解释，但它们不能被分离出来。(2)利用稳定高配位化合物的Martin配体C_6H_5(CF_3)_2（OH）合成了Wittig和Peterson反应的中间体五配位草磷烷和草硅烷，并用x射线晶体学确定了它们的结构。对它们的热裂解反应进行了研究，揭示了Wittig和Peterson反应的机理。(3)合成重14族和重16族元素（酮的重同系物）之间有双键的化合物，TbArM=X(M=Si, Ge, Sn; Tb=2,4,6-tris[bis（三甲基硅基）甲基]phenyl；研究了Ar=甲酰基或2,4,6-三异丙基苯基（Tip）。分离得到了第一个稳定的德耳曼硫酮Tb(Tip) Ge=S，并通过x射线晶体学确定了其结构。它对非常活泼的Ge=S键进行了各种加成和环加成。

In this study the following three projects were carried out. (1) Synthesis of stable silicenium ions and their reactivities. (2) Synthesis and reactivities of penta-coordinate oxaphosphetanes and oxasiletanides. (3) Synthesis and reactivities of double-bond compounds between group 14 and group 16 elements.(1) Synthesis of silicenium ions (ArX)_3Si^+(X=S, Se ; Ar=2,4,6-tri-t-butylphenyl) and mes_3Si^+ was carried out by the reaction of (ArX)_3SiCl with AgClo_4 and that of Mes_3 SiCl with SbCl_5. Both reactions gave products explicable in terms of the intermediary of silicenium ions, but they could not be isolated.(2) Penta-coordinate oxaphosphetanes and oxasiletanides, intermediates of the Wittig and Peterson reactions, respectively, were synthesized by taking advantage of the Martin ligand C_6H_5(CF_3)_2(OH) which is known to stabilize high-coordinate compounds, and their structures were established by X-ray crystallography. An study on their thermolyses revealed the mechanism of the Wittig and Peterson reactions.(3) Synthesis of compounds having a double bond between heavy group 14 and group 16 elements (heavy congeners of a ketone), TbArM=X(M=Si, Ge, Sn ; Tb=2,4,6-tris[bis(trimethylsilyl)methyl] phenyl ; Ar=mesityl or 2,4,6-triisopropylphenyl(Tip)) was studied. The first stable germanethione, Tb(Tip) Ge=S, was isolated and its structure was established by X-ray crystallography. It underwent various additions and cycloadditions oward the very reactive Ge=S bond.