One Collision—Two Substituents: Gas‐Phase Preparation of Xylenes under Single‐Collision Conditions

• Published in: Angewandte Chemie Vol. 136; no. 5
• Main Authors: Medvedkov, Iakov A., Nikolayev, Anatoliy A., He, Chao, Yang, Zhenghai, Mebel, Alexander M., Kaiser, Ralf I.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 25.01.2024
• Subjects: 1,3-Butadiene; Aromatic compounds; Astrochemistry; Asymptotic giant branch stars; Butadiene; Chemistry; Combustion; Electronic structure; Extraterrestrial environments; Extreme environments; Gas-Phase Reactions; Hydrogen; Isomerization; Isoprene; Molecular beams; Molecular clouds; Neptune satellites; Planetary atmospheres; Propynyl; Reaction Mechanisms; Stellar envelopes; Stereochemistry; Xylene
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202315147

The fundamental reaction pathways to the simplest dialkylsubstituted aromatics—xylenes (C6H4(CH3)2)—in high‐temperature combustion flames and in low‐temperature extraterrestrial environments are still unknown, but critical to understand the chemistry and molecular mass growth processes in these extreme environments. Exploiting crossed molecular beam experiments augmented by state‐of‐the‐art electronic structure and statistical calculations, this study uncovers a previously elusive, facile gas‐phase synthesis of xylenes through an isomer‐selective reaction of 1‐propynyl (methylethynyl, CH3CC) with 2‐methyl‐1,3‐butadiene (isoprene, C5H8). The reaction dynamics are driven by a barrierless addition of the radical to the diene moiety of 2‐methyl‐1,3‐butadiene followed by extensive isomerization (hydrogen shifts, cyclization) prior to unimolecular decomposition accompanied by aromatization via atomic hydrogen loss. This overall exoergic reaction affords a preparation of xylenes not only in high‐temperature environments such as in combustion flames and around circumstellar envelopes of carbon‐rich Asymptotic Giant Branch (AGB) stars, but also in low‐temperature cold molecular clouds (10 K) and in hydrocarbon‐rich atmospheres of planets and their moons such as Triton and Titan. Our study established a hitherto unknown gas‐phase route to xylenes and potentially more complex, disubstituted benzenes via a single collision event highlighting the significance of an alkyl‐substituted ethynyl‐mediated preparation of aromatic molecules in our Universe. This study uncovers gas‐phase synthesis of xylenes through an isomer‐selective reaction of 1‐propynyl radical with C5H8 isomers (2‐methyl‐1,3‐butadiene, 1,3‐pentadiene). Our study established a hitherto unknown gas‐phase route to xylenes and potentially more complex, disubstituted benzenes via a single collision event highlighting the significance of an alkyl‐substituted ethynyl‐mediated preparation of aromatic molecules in our Universe.