TY - JOUR
T1 - 1H NMR observation of trimethylsilyl migration in gas phase 5-Trimethylsilylcyclopentadiene
AU - Taha, A. N.
AU - Moreno, P. O.
AU - LeMaster, C. B.
AU - LeMaster, C. L.
AU - True, N. S.
PY - 2000/10/10
Y1 - 2000/10/10
N2 - Gas-Phase 1H NMR spectra of a sample containing 4 Torr of trimethylsilylcyclopentadiene, 1 Torr of CHCl3, and 707 Torr SF6 show exchange broadened line shapes consistent with the degenerate migration of the trimethylsilyl group in the 5-Isomer via 1-2 sigmatropic shifts. The kinetic parameters for this process in the gas phase, ΔH(+) = 15.4(0.2) kcal mol-1, ΔS(+) = -1.1(0.1) kcal mol-1, and ΔG(+) = 15.7 kcal mol-1 are slightly higher than values reported previously for the neat liquid. The small solvent effect observed indicates that a large charge separation in the transition state is unlikely. (C) 2000 Elsevier Science B.V.
AB - Gas-Phase 1H NMR spectra of a sample containing 4 Torr of trimethylsilylcyclopentadiene, 1 Torr of CHCl3, and 707 Torr SF6 show exchange broadened line shapes consistent with the degenerate migration of the trimethylsilyl group in the 5-Isomer via 1-2 sigmatropic shifts. The kinetic parameters for this process in the gas phase, ΔH(+) = 15.4(0.2) kcal mol-1, ΔS(+) = -1.1(0.1) kcal mol-1, and ΔG(+) = 15.7 kcal mol-1 are slightly higher than values reported previously for the neat liquid. The small solvent effect observed indicates that a large charge separation in the transition state is unlikely. (C) 2000 Elsevier Science B.V.
KW - 5-Trimethylsilylcyclopentadiene
KW - H NMR
KW - Degenerate migration
UR - https://www.scopus.com/pages/publications/0034633561
U2 - 10.1016/S0022-2860(00)00549-4
DO - 10.1016/S0022-2860(00)00549-4
M3 - Article
AN - SCOPUS:0034633561
SN - 0022-2860
VL - 553
SP - 37
EP - 42
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
IS - 1-3
ER -