title: Substituent effects in the interconversion of phenylcarbene, bicyclo[4.1.0]hepta-2,4,6-triene, and 1,2,4,6-cycloheptatetraene.
abstract: The effect of aryl substituents on the interconversion of phenylcarbene (PC), bicyclo[4.1.0]hepta-2,4,6-triene (BCT), and 1,2,4,6-cycloheptatetraene (CHTE) has been studied by density functional theory. It is found that substituents have a large effect on both the thermochemistry and activation energy of these rearrangements. For instance, para-substitution yields a range of overall activation energies for the formation of BCT from PC of 20.3 to 11.7 kcal/mol for the NH(2) and NO(2) substituents, respectively. In the syn-meta-substituted cases, all of the rearrangements to the substituted CHTE species are more exothermic than that of the parent PC. The proximity of the substituent to the carbene center can also affect the overall chemistry as in the case of ortho-substituted species. Here, formation of bicyclic structures and ylides, which can then rearrange to stable structures, can compete with the ring-expansion process. Also, as calculated herein, the ortho substituents can, by a combination of mesomeric and steric interactions with the carbene center, affect the overall barrier to reversible ring expansion. Most notably, in the anti-ortho-substituted species, halogens (F and Cl) raise the activation barrier to ring expansion by approximately 5 kcal/mol. This is reminiscent of the effect of fluorine substitution on the chemistry (inter- and intramolecular) of phenylnitrene.
authors.affiliation: Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, OH 43210, USA.
authors.forename: C Michael
authors.initials: CM
authors.lastname: Geise
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Hadad