Fg. Riddell et M. Rogerson, THE DOUBLE TERT-BUTYL ROTATION IN SOLID S-2-TERT-BUTYL-5-(TERT-BUTYLSULPHONYL)-1,3-DIOXANE, Magnetic resonance in chemistry, 35(5), 1997, pp. 333-336
s-2-tert-Butyl-5-(tert-butylsulphonyl)-1,3-dioxane displays a double t
ert-butyl coalescence at low temperatures in its C-13 CP/MAS NMR spect
rum associated with slowing down of the rotation of both tert-butyl gr
oups. The overlap of the resonances precluded the measurement of rates
of rotation from Lineshape analyses. However, C-13 T-1 rho measuremen
ts above coalescence allowed rates of rotation and activation paramete
rs for the rotations of both groups to be derived. The C-tert-butyl gr
oup has Delta H-double dagger = 26.3 +/- 3.6 kJ mol(-1) and Delta S-do
uble dagger - 13 +/- 14 J K-1 mol(-1). The S-tert-butyl group has Delt
a H-double dagger = 31.8 +/- 2.2 kJ mol(-1) and Delta S-double dagger
- 9 J K-1 mol(-1). (C) 1997 by John Wiley & Sons, Ltd.