Gas-Phase Synthesis of 3-Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2 Π) with 1,3-Butadiene (CH2 CHCHCH2 ; X1 Ag ).

Abstract

The crossed molecular beam reactions of the methylidyne radical (CH; X2 Π) with 1,3-butadiene (CH2 CHCHCH2 ; X1 Ag ) along with their (partially) deuterated counterparts were performed at collision energies of 20.8 kJ mol-1 under single collision conditions. Combining our laboratory data with ab initio calculations, we reveal that the methylidyne radical may add barrierlessly to the terminal carbon atom and/or carbon-carbon double bond of 1,3-butadiene, leading to doublet C5 H7 intermediates with life times longer than the rotation periods. These collision complexes undergo non-statistical unimolecular decomposition through hydrogen atom emission yielding the cyclic cis- and trans-3-vinyl-cyclopropene products with reaction exoergicities of 119±42 kJ mol-1 . Since this reaction is barrierless, exoergic, and all transition states are located below the energy of the separated reactants, these cyclic C5 H6 products are predicted to be accessed even in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and cold molecular clouds such as TMC-1.