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

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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.