Basic Studies on Photo- and Thermal-Reactions of 14 Group Metal Compounds

14族金属化合物的光热反应基础研究

基本信息

批准号：
02640387
负责人：
NAKADAIRA Yasuhiro
金额：
$ 1.34万
依托单位：
University of Electro-Communications
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

项目摘要

1.185 nm photolysis of octamethyltrisilane, hexamethyldisilane, and tetrabutylsilaneIn the trisilane, elimination of dimethylsilylene competes favorably with homolysis of Si-Si bonds. In the disilane, homolysis of the Si-Si bond prevails over silylene generation, which is confirmed by detection of tetramethylsilane and the trapping experiment. In the monosilane, cleavage of Si-C bonds predominates but a trac7e of dibutylsilylene is detected by the trapping experiment.2.185 nm photolysis of hexamethyldigermanePhotochemical behavior of the digermane has been shown t'o be qu ite similar to those of the 'corresponding silicon analog, but the elimination of the divalent species is much more effective in the germanium analog.3. Photolysis of aryl-substituted 14 group metal catenates, PhMe_2E-E'Me_3 (E, E' = Si, Ge)Photolysis of PhMe_2SiGeMe_3, PhMe_2GeSiMe_3, and PhMe_2GeGeMe_3 have been examined. Their photochemical behavior can be rationalized by the radical pair generated by homolysis of the E-E' bond.4. Analogy between photo-induced electron transfer reaction and the mass spectral fragmentationMass spectra of polysilaalkanols are rationalized based on their chemical reactivities under photo-induced electron transfer conditions.5. Photo-induced transfer reaction of trifluoromethyl-substituted benzenes with hexamethyldisilane and octamethyltrisilaneUnder these conditions, substitution of the fluorine with the silyl function, and silylation of the aromatic ring have shown to take place.

1.185 NM八甲基三硅烷，六甲基二硅烷和四丁硅烷的光解在三硅烷中，消除了二甲基二甲硅烷基二甲基二甲硅烷，与Si-Si键的均匀分解竞争。在Diasilane中，Si-Si键的同叶占据了甲硅烷基的生成，这是通过检测四甲基硅烷和捕获实验证实的。在单硅烷中，通过捕获实验检测到Si-C键的切割，但二丁基甲硅烷基的TRAC7E被检测到。2.185nm的六甲基甲甲中非类化学行为的光解已经表明，远离二甲烷的二甲基甲基甲烷的分解与'相似的替代替代的替代替代的替代了较大的有效的替代的替代的孤立的，但有效地划分了，但要划分了较大的划分，但划分了划分的划分，施法了划分的划分，但划分了划分的施法。模拟3。芳基取代的14组金属甲壳虫的光解，PHME_2SIGEME_3，PHME_2GESIME_3和PHME_2GEGEME_3的PHME_2E-E'ME_3（E，E'= SI，GE）的光解。他们的光化学行为可以通过E-E'键的同层产生的自由基对合理化。4。光诱导的电子转移反应与多硅烷酚的质谱片段谱之间的类比，基于光诱导的电子传递条件下的化学反应率合理化。5。光诱导的三氟甲基取代的苯与六甲基二硅烷和八甲基三乙烷的转移反应，这些条件取代了氟通过甲硅烷基的功能，并且芳族环的硅烷基化已经发生。