Tris(trimethylsilyl)silane (TTMSS)-Derived Radical Reactivity toward Alkenes:  A Combined Quantum Mechanical and Laser Flash Photolysis Study

The reactivity of the tris(trimethylsilyl)silane (TTMSS)-derived radical is studied through an approach combining laser flash photolysis and quantum mechanical calculations. The results obtained for TTMSS are compared both to a classical silyl radical derived from triethylsilane and to a previously studied carbon-centered structure. Different worthwhile results are obtained: (i) the addition and hydrogen abstraction rate constants are directly measured, (ii) the high reactivity and the low selectivity of TTMSS toward the addition to alkenes are perfectly explained by antagonist polar and enthalpy effects, (iii) efficient hydrogen abstraction reactions from antioxidants such as vitamin E are observed, and (iv) TTMSS is seen to also act as an efficient initiator for the polymerization of an acrylate monomer.