Preliminary communicationKinetic study on thermal syn-anti isomerization of dodecaisopropyltricyclo[4.2.0.02,5]octasilane

Add time:09/02/2019    Source:sciencedirect.com

When heated at 493 K, syn-dodecaisopropyltricyclo[4.2.0.02,5]octasilane (syn-1) isomerizes to anti-dodecaisopropyltricyclo[4.2.0.02,5]octasilane (anti-1); isomerization of anti-1 to syn-1 does not occur at 493 K. Thermodynamic parameters were determined for the one-way isomerization of syn-1 to anti-1: Ea = 42.3 kcal mol−1, log A = 15.1 s−1, ΔH‡ = 41.4 kcal mol−1, ΔS‡ = 7.6 × 10−3 kcal mol−1 K−1 and ΔG493 K‡ = 37.6 kcal mol−1. The activation energy is considerably larger than that for the analogous thermal isomerization of syn-tricyclo[4.2.0.02.5]octane (syn-2) to anti-tricyclo[4.2.0.02.5]octane (anti-2), indicating that the bond dissociation energy of the bridgehead SiSi bond of syn-1 is larger than that of the bridgehead CC bond of syn-2.

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