Elimination reactions. Part IV. Heavy atom isotope effects in ElcB elimination reactions
โ Scribed by F.M. Fouad; P.G. Farrell; A.G. Abdel-Rehiem
- Publisher
- Elsevier Science
- Year
- 1974
- Tongue
- French
- Weight
- 184 KB
- Volume
- 15
- Category
- Article
- ISSN
- 0040-4039
No coin nor oath required. For personal study only.
โฆ Synopsis
Received ia BSA 9 l&y 1974; raoeiwd in UK for pablioation 6 An6unt 1974) Although heavy-atom isotope effects have been widely used in mechanistic studies of substitution reactions, little work has been reported 2 on their use in studies of elimination reactions . In the latter, studies of these effects hold promise for the identification of the degree of bond extension (or bond breakage) in the rate determining step and thus for the investigation of reactions which lie close to the mechanistic borderlines between El, or ElcB, and E2 reactions. We have been unable to find any examples of heavy atom isotope effects in ElcB eliminations and report here our preliminary studies of the 14 C leaving group effects in HCN elimination from the polycyanoethanes (I) and (II). Studies of the magnitude of such effects in ElcB eliminations, and the factors affecting them, are necessary prerequisites for their use in mechanistic interpretations.
๐ SIMILAR VOLUMES
## Abstract A convenient approach to compute kinetic isotope effects (KIEs) in condensed phase chemical reactions is via path integrals (PIs). Usually, the primitive approximation is used in PI simulations, although such quantum simulations are computationally demanding. The efficiency of PI simula
The intramolecular elimination of isobutene from 2-d,-triisobutylaluminum has been studied in the gas phase for temperatures ranging between 102.4 and 184.6'C. The reaction is apparently homogeneous and obeys the first order rate law, yielding the following Arrhenius relationship: log kelim (sec-')