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36'52-55 This may reflect the importance of post-HF electron correlation corrections for the proper description of the barrier since the LDF approach, formulated in terms of electron density rather than electron orbitals, incorporates some electron correlation effects. As we showed recently, the inclusion of correlation effects at the MP2/631G level significantly increases the HF barriers for curved surface hydrocarbons by approximately 5--6 kcal/mol. 36 Table 3. 91 55 53 21 Exp. 87 8 Molecular Mechanics MM2PI(1977) MOMM(1987) MM2/87 Semi-empirical MO Polynuclear Aromatic Hydrocarbons with Curved Surfaces 23 Minimum energy conformations of 8 are reasonably well reproduced by most of the commonly used computational methods.
Cycloproparenes via Adducts of Dihalocarbenes to Cyclohexa-1,4-dienes Aromatization of dihalocarbene adducts to 1,4-cyclohexadiene or synthetic equivalents is the method Of choice for the synthesis of the parent benzocyclopropene (1). 0]hept-2-ene (51) has been shown by labeling experiments with 51 depleted of 13C at C7, to proceed via a series of elimination and double bond migration steps via cyclopropene- and alkylidenecyclopropane intermediates 52 to 54 with preservation of the original carbon skeleton.
36 For condition (b), some entropy contribution to the barrier for inversion in corannulene is expected due to the different symrrietries of the planar and bowl-shaped 8. This contribution is equal t o - R In t~* + R In t~, where t~* and ~ denote the symmetry numbers of the TS and the substrate. The symmetry numbers for the planar TS and nonplanar 8 (substrate) are 10 and 5, respectively. deg, which increases AG* by ca. 4 kcal/mol at room temperature. 6 kcal/mol after considering both thermal and zero point energy corrections to AH* as well as vibrational and rotational entropies of the planar and nonplanar conformers.