Abstract
A thermal reaction scheme for the rearrangement of trimethylsilylsilylene (Me3Si−S̈i−H) proposed in a previous study [Organometallics 1986, 5, 698] was studied by the MP2 and DFT methods. The reaction pathways were searched by intrinsic reaction coordinate analysis. We report structures and energies of various silicon species. Activation energies for the C−H insertions by the divalent silicon centers in Me2HSiCH2−S̈i−H and MeHSiCH2−S̈i−Me are predicted to be high, 121 and 110 kJ/mol, respectively, in excellent agreement with an experimental value of 121 kJ/mol. However, the energy barrier for the C−H insertion by the divalent silicon center in Me3S−S̈i−H, predicted to be relatively small, 53 kJ/mol, is lower than that for the 1,2-Me shift (78 kJ/mol) in Me3Si−S̈i−H.
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