Reaction of Triethylsilyl Radical with Sulfides, a Laser Flash Photolysis Study

Reaction of Triethylsilyl Radical with Sulfides, a Laser Flash Photolysis Study

Triethylsilyl radical was generated by laser flash photolysis of a 1:1 (v/v)solution of triethylsliance and di-tert-butyl peroxide. The silicon centered radical was reacted with sulfides to give carbon centered radicals by displacement at sulfar. The carbon radicals were readily detected by their transient absorption spectra. The absolute rate of reaction of triethylsilyl radical with 9-fluorenylphenylsulfide, di-n-butylsulfide, di-sec-butyl, di-tert-butyl sulfide and di-n-butyl disulfide are $2.40{\pm}0.12{\times}10^8M^{-1}s^{-1}$, $11.21{\pm}0.89{\times}10^6M^{-1}s^{-1}$, $8.79{\pm}0.73{\times}10^6M^{-1}s^{-1}$, $3.29{\pm}0.18{\times}10^6M^{-1}s^{-1}$, and $3.41{\pm}0.09{\times}10^8M^{-1}s^{-1}$, respectively.