A chemical dynamics study of the reaction of the methylidyne radical (CH, X2Π) with dimethylacetylene (CH3CCCH3, X1A1g)

Abstract

The gas-phase reaction of the methylidyne (CH; X²Π) radical with dimethylacetylene (CH₃CCCH₃; X¹A_1g) was studied at a collision energy of 20.6 kJ mol⁻¹ under single collision conditions with experimental results merged with ab initio calculations of the potential energy surface (PES) and ab initio molecule dynamics (AIMD) simulations. The crossed molecular beam experiment reveals that the reaction proceeds barrierless via indirect scattering dynamics through long-lived C₅H₇ reaction intermediate(s) ultimately dissociating to C₅H₆ isomers along with atomic hydrogen with atomic hydrogen predominantly released from the methyl groups as verified by replacing the methylidyne with the D1-methylidyne reactant. AIMD simulations reveal that the reaction dynamics are statistical leading predominantly to p28 (1-methyl-3-methylenecyclopropene, 13%) and p8 (1-penten-3-yne, 81%) plus atomic hydrogen with a significant amount of available energy being channeled into the internal excitation of the polyatomic reaction products. The dynamics are controlled by addition to the carbon–carbon triple bond with the reaction intermediates eventually eliminating a hydrogen atom from the methyl groups of the dimethylacetylene reactant forming 1-methyl-3-methylenecyclopropene (p28). The dominating pathways reveal an unexpected insertion of methylidyne into one of the six carbon–hydrogen single bonds of the methyl groups of dimethylacetylene leading to the acyclic intermediate, which then decomposes to 1-penten-3-yne (p8). Therefore, the methyl groups of dimethylacetylene effectively ‘screen’ the carbon–carbon triple bond from being attacked by addition thus directing the dynamics to an insertion process as seen exclusively in the reaction of methylidyne with ethane (C₂H₆) forming propylene (CH₃C₂H₃). Therefore, driven by the screening of the triple bond, one propynyl moiety (CH₃CC) acts in four out of five trajectories as a spectator thus driving an unexpected, but dominating chemistry in analogy to the methylidyne – ethane system.