Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 12, Issue 24, Pages 6323-6330Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200501517
Keywords
density functional calculations; dyotropic rearrangements; stereoelectronic effects; synchronicity
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The effects of different substituents on type I-dyotropic rearrangements of open-chain and cyclic 1,2-dibromo hydrocarbons have been studied by means of DFT calculations. The activation energy (Ea) of this transformation decreases with the pi-donor ability of the substituent attached to the reacting ethylenic system. This is due to donation of electronic density by conjugation or hyperconjugation. This donation leads to longer C-C and C-Br bond lengths in the corresponding four-membered transition states (TSs). Linear relationships between the E. and either the up Hammett substituent constants and the C-C bond length of the TSs were also found. In all cases, the processes have a high value of synchronicity, which is mainly independent on the substituents. A model based on the second-order perturbational analysis for one ethylene unit with two apical bromine radicals accounts for all the computed results.
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