Directed Gas-Phase Synthesis of Triafulvene under Single-Collision Conditions

The triafulvene molecule (c-C₄ H₄ )-the simplest representative of the fulvene family-has been synthesized for the first time in the gas phase through the reaction of the methylidyne radical (CH) with methylacetylene (CH₃ CCH) and allene (H₂ CCCH₂ ) under single-collision conditions. The experimental and computational data suggest triafulvene is formed by the barrierless cycloaddition of the methylidyne radical to the π-electron density of either C₃ H₄ isomer followed by unimolecular decomposition through elimination of atomic hydrogen from the CH₃ or CH₂ groups of the reactants. The dipole moment of triafulvene of 1.90 D suggests that this molecule could represent a critical tracer of microwave-inactive allene in cold molecular clouds, thus defining constraints on the largely elusive hydrocarbon chemistry in low-temperature interstellar environments, such as that of the Taurus Molecular Cloud 1 (TMC-1).