A Study on the Reducing Abilities of Tris(alkylthio)silanes

Article abstract of DOI:10.1021/jo00034a042

Tris(methylthio)silane and tris(isopropylthio)silane effectively reduce a variety of organic substrates via free radical mechanisms.These silanes can also be used as hydrosilylating agents for alkenes having electron-donating substituents.The bond dissociation energy of the Si-H bonds have been measured by photoacoustic calorimetry and found to be around 83 kcal mol^-1.The absolute rate constants for the reaction of the tert-butoxyl radical with (RS)3SiH have been measured by a laser flash photolysis technique and the optical absorption spectra of the correspondingradicals have been obtained.Multiple scattering X_α calculations showed that the dominant absorption detected in the UV-vis region was due to ?_Si-S(e) -> SOMO and SOMO -> ?^*_Si-S(e) transitions.