Thermal Transformation of Ring-Opened [2 2] C60 Dimer into a Wide-Bridged C120 Isomer. A Computational Evaluation of Fulvalene-Naphthalene Rearrangements |
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Authors: | Kazuhiko Honda Eiji ૿ sawa Zdenek Slanina Takatoshi Matsumoto |
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Affiliation: |
a Computational Chemistry Group, Department of Knowledge-Based Information Engineering, Toyohashi University of Technology, Toyohashi, Japan
b Department of Chemistry, National Chung-Cheng University, Taiwan ROC |
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Abstract: | As a continuation of the studies on thermal transformation of the 2+2] C60 dimer (1), the consequence of the pyracylene-rearrangement-like valence isomerization of the fulvalene partial structure at the bridge of the ring-opened product from 1, namely 2, was searched by dynamic reaction coordinate /AM1 semiempirical MO calculations. It is predicted that the fulvalene bridge of 2 rearranges into naphthalene partial structure by the concerted 'in-plane' mechanism to give a wide-bridged C120 intermediate having twenty five-membered rings and two ten-membered rings (3). The computed energy of activation (145 kcal/mol) is 40 kcal/mol lower than those computed for pyracylene rearrangements. In contrast, the recently reported analogous rearrangement of indigo (13) to dibenzonaphthyridindione (14) is computed to occur by the stepwise 'sp3' mechanism. |
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