Dispersion Interaction Stabilizes Sterically Hindered Double Fullerenes |
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| Authors: | Jun Zhang Prof?Dr Michael Dolg |
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| Affiliation: | Institute for Theoretical Chemistry, University of Cologne, Address Greinstr. 4, 50939 Cologne |
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| Abstract: | By state‐of‐the‐art quantum chemical methods, we show that for bulky functional groups like cyclohexane, 20]fullerene, dodecahedrane, and C60, the attractive dispersion interaction can have a greater impact on stereochemistry than the repulsive steric effect, making the compact isomer the more stable one. In particular, for the double C60 adduct of pentacene 1 , the syn isomer should be the main product instead of the anti one inferred in the original synthesis experiment (Y. Murata et al., J. Org. Chem. 1999 , 64, 3483). With and without dispersion interactions taken into account, the Gibbs energy difference ΔG(syn?anti) is ?6.36 and +1.15 kcal mol?1, respectively. This study reminds us that dispersion interactions as well as electrostatic or hyperconjugation effects, etc. can lead to some unusual stereochemical phenomena. |
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| Keywords: | dispersion interactions fullerenes isomer stability steric effects van der Waals forces |
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