Gas-Phase Formation of Fulvenallene (CH) via the Jahn-Teller Distorted Tropyl (CH) Radical Intermediate under Single-Collision Conditions.

The fulvenallene molecule (CH) has been synthesized via the elementary gas-phase reaction of the methylidyne radical (CH) with the benzene molecule (CH) on the doublet CH surface under single collision conditions. The barrier-less route to the cyclic fulvenallene molecule involves the addition of the methylidyne radical to the π-electron density of benzene leading eventually to a Jahn-Teller distorted tropyl (CH) radical intermediate and exotic ring opening-ring contraction sequences terminated by atomic hydrogen elimination. The methylidyne-benzene system represents a benchmark to probe the outcome of the elementary reaction of the simplest hydrocarbon radical-methylidyne-with the prototype of a closed-shell aromatic molecule-benzene-yielding nonbenzenoid fulvenallene. Combined with electronic structure and statistical calculations, this bimolecular reaction sheds light on the unusual reaction dynamics of Hückel aromatic systems and remarkable (polycyclic) reaction intermediates, which cannot be studied via classical organic, synthetic methods, thus opening up a versatile path to access this previously largely obscure class of fulvenallenes.