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The Chemistry of Inter-element Unsaturated Linkage

元素间不饱和键化学

基本信息

批准号：
09239101
负责人：
YOSHIFUJI Masaaki
金额：
$ 55.68万
依托单位：
TOHOKU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 2000
项目状态：
已结题

项目摘要

1. Desulfurization reaction of a dithioxophosphorane bearing the 2,4-di-t-butyl-6-methylphenyl group as protecting moiety gave the corresponding dithioxophosphine, which slowly trimerized to trithiatriphosphinane and isolated.2. Photoisomerization of a 1-tris (trialkylsilyl) cyclotrisilene proceeded to give the corresponding bicyclo [1.1.0] tetrasilane, and the addition of an alcohol occurred in the anti-addition mode. Furthermore, as byproduct, the spiropentasiladiene derivative was isolated and characterized.3. A cyclotrigermenium ion, constituting the 3-membered 2-π electron aromatic system, reacted with a bulky nucleophile to give a cyclotrigermene, unsymmetrically substituted at the saturated germanium atom. It was found that the conformation around the double bond depends on the electronic and steric effects of the substituent.4. Thermal reaction of penta-coordinated 1,2-oxasiletanides bearing the Martin ligand were studied in the presence of acetic acid or 1, 1, 1-trifluoroethanol as proton source. 1,2-Oxasiletanides is considered to be a reaction intermediate, which serves for the Peterson reaction and the homo-Brook rearrangement depending upon the bulkiness at the 3-position as well as the acidity of the proton source.5. Utilizing the 2,6-bis [bis (trimethylsilyl) methyl)-4-[tris (trimethylsilyl) methyl] phenyl group, a novel stibabismuthene as a double bond compound between two different group 15 elements, was prepared and characterized.6. Taking the electronic and steric effect of substituents into account, a real triple bond compounds of silicon, disilyne, has been proposed to be stabilized, by theoretical calculation. Similarly triple bonds containing germanium, tin, and lead ware calculated as well as silanaphthalene and silabenzene.

1.以2，4-二叔丁基-6-甲基苯基为保护基的二硫代氧代膦进行脱硫反应，生成相应的二硫代氧代膦，缓慢三聚生成三硫代三膦并分离. 1-三（三烷基甲硅烷基）环三硅烯的光异构化进行，得到相应的双环[1.1.0]四硅烷，和醇的加成发生在反加成模式。此外，作为副产物的螺环戊二烯衍生物被分离和表征.环三锗烯离子构成三元2 π电子芳香体系，与大体积亲核试剂反应，得到饱和锗原子上不对称取代的环三锗烯。发现取代基的电子效应和空间效应决定了双键周围的构象.以乙酸或三氟乙醇为质子源，研究了带有Martin配体的五配位1，2-氧杂硅杂环丁烷的热反应。1，2-Oxasiletanides被认为是一种反应中间体，根据3-位的体积以及质子源的酸性，它可用于Peterson反应和homo-Brook重排反应。5.利用2，6-双[双（三甲基硅基）甲基）-4-[三（三甲基硅基）甲基]苯基，合成并表征了一种新的锑铋烯，它是两种不同的15族元素之间的双键化合物.通过理论计算，考虑到取代基的电子效应和空间位阻效应，提出了一种真实的硅三键化合物二硅炔的稳定化方法。类似地，计算了含锗、锡和铅的三键以及硅萘和硅苯。