Abstract
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.
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