The mechanism and energetics of insertion reactions of silylenes.
56 insertion reactions between seven silylenes and eight reactants were investigated using B3LYP/cc-pVTZ method. The reaction energies and the stability of the silylenes are in good correlation. Silaimidazole-2-ylidene gives the highest reaction energies while Kira's stable five membered ring dialkylsilylene shows the smallest reaction energies. All the reaction energies and activation energies of the six-membered ring diazasilylene ({HC[CMeN(R)](2)}Si, R = 2,6-diisopropylphenyl) were found equal to that of the saturated five-membered diazasilole. The sum of the reaction free energies (ΔG) and activation free energies (ΔG(‡)) of a reaction depend on the reactant but are independent of the silylene.
Nyíri
Kinga
K
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, (BUTE), Szent Gellért tér 4, 1521, Budapest, Hungary.
Szilvási
Tibor
T
Veszprémi
Tamás
T