Gas-Phase Formation of Fulvenallene (C7H6) via the Jahn–Teller Distorted Tropyl (C7H7) Radical Intermediate under Single-Collision Conditions

• DOI: 10.1021/jacs.9b13269
• Publication Date: 2020-01-21T14:52:51Z
• Authors: Chao He; Aaron M. Thomas; Galiya R. Galimova; Alexander N. Morozov; Alexander M. Mebel; Ralf I. Kaiser
• Keywords: 02 engineering and technology; 0210 nano-technology

The fulvenallene molecule (C7H6) has been synthesized via the elementary gas-phase reaction of methylidyne radical (CH) with benzene (C6H6) on doublet C7H7 surface under single collision conditions. barrier-less route to cyclic involves addition π-electron density leading eventually a Jahn-Teller distorted tropyl (C7H7) intermediate and exotic ring opening-ring contraction sequences terminated by atomic hydrogen elimination. methylidyne-benzene system represents benchmark probe outcome simplest hydrocarbon radical-methylidyne-with prototype closed-shell aromatic molecule-benzene-yielding nonbenzenoid fulvenallene. Combined electronic structure statistical calculations, this bimolecular sheds light unusual dynamics Hückel systems remarkable (polycyclic) intermediates, which cannot be studied classical organic, synthetic methods, thus opening up versatile path access previously largely obscure class fulvenallenes.