83958-00-3Relevant articles and documents
Thermolabile Hydrocarbons, XVI. Thermal Stability, Strain Enthalpy, and structure of Sym. Tetrasubstituted Ethanes
Hellmann, Goetz,Hellmann, Siegried,Beckhaus, Hans-Dieter,Ruechardt, Christoph
, p. 3364 - 3383 (2007/10/02)
Activation parameters were determined for the thermolysis reaction of 12 sym. substituted ethanes ( Ct - Ct series).From product analysis it was concluded that the central Ct - Ct bond is cleaved in the rate determing step by homolysis.The correlation between δH* and the change in strain enthalpy during the activation process (MM2 calculations) points to nearly 20percent residual strain at transition state.From a comparison of the thermolysis data for Ct - Ct and Cq - Cq ethanes a 2.3 kcal/mol difference in stabilization energy for sek. and tert. alkyl radicals is derived as an upper limiting value.The influence of strain on bond lengths, bond angles, and torsional angles is compared for Ct - Ct and Cq - Cq ethanes.