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The Triplet Surface of the Zimmerman Di-π-Methane Rearrangement of Dibenzobarrelene

Authors

  • Dr. Ricardo A. Matute,

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA)
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  • Prof. Dr. Kendall N. Houk

    Corresponding author
    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA)
    • Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA)
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  • We are grateful to the National Science Foundation (grant number CHE-0548209) for financial support of this research. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation grant number OCI-1053575. Computer time was also provided by the UCLA Institute for Digital Research and Education (IDRE). R.A.M. acknowledges the financial support from CONICYT and BECAS CHILE.

Abstract

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High-level calculations: The Zimmerman di-π-methane rearrangement of dibenzobarrelene occurs via a triplet state to form dibenzosemibullvalene, overcoming two barriers connecting two biradicals. The shape of the triplet potential-energy surface shows that the rearrangement involves two transition states. The first triplet diradical intermediate may bypass in the passive of the alkene triplet to the final intermediate (see picture).

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