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

1.185 nm光解八甲基三硅烷、六甲基二硅烷和四丁基硅烷在三硅烷中，二甲基硅烷的消除有利于硅硅键的均解。在二硅烷中，Si-Si键的均裂比硅烯的生成更重要，这一点通过四甲基硅烷的检测和捕集实验得到了证实。在单硅烷中，Si-C键的断裂占主导地位，但通过捕获实验检测到二丁基硅烯的踪迹。在2.185 nm光解六甲基双双曼的光化学行为表明，双双曼的光化学行为与相应的硅类似物非常相似，但在锗类似物中，二价物质的消除更为有效。研究了芳基取代的14基团金属螯合物phme_2e’me_3 （E， E’= Si, Ge）、PhMe_2SiGeMe_3、PhMe_2GeSiMe_3和PhMe_2GeGeMe_3的光解。它们的光化学行为可以用E-E键均解产生的自由基对来解释。光诱导电子转移反应与质谱片段化的类比根据聚硅烷醇在光诱导电子转移条件下的化学反应活性，对其质谱进行了合理化。三氟甲基取代苯与六甲基二硅烷和八甲基三硅烷的光诱导转移反应在此条件下，氟被硅基取代，芳香环被硅基化。

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.