![]() ![]() ![]() Gas-phase neutral methyl formate can be produced from its protonated counterpart through either a dissociative electron recombination reaction or a proton transfer reaction to a molecule with larger proton affinity. The proposed reactions, acid-catalyzed Fisher esterification and methyl cation transfer, both produce the less stable trans-conformational isomer of protonated methyl formate in relatively high abundance under the kinetically controlled conditions relevant to interstellar chemistry. Motivated by these findings, two new gas-phase ion-molecule formation routes are proposed and characterized using electronic structure theory with conformational specificity. Yet, recent chemical imaging studies of methyl formate and molecules potentially related to its formation suggest that it may form through previously unexplored gas-phase chemistry. ![]() Previous studies of potential formation pathways for methyl formate in interstellar clouds ruled out gas-phase chemistry as a major production route, and more recent chemical kinetics models indicate that it may form efficiently from radical–radical chemistry on ice surfaces. Methyl formate presents a challenge for the conventional chemical mechanisms assumed to guide interstellar organic chemistry.
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