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

Journal Article · 20 January 2020 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b13269 · OSTI ID:1603232

He, Chao ^[1]; Thomas, Aaron M.  ^[2]; Galimova, Galiya R. ^[3]; Morozov, Alexander N. ^[4]; Mebel, Alexander M.  ^[4]; Kaiser, Ralf I.  ^[2]

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1. Univ. of Hawaii at Manoa, Honolulu, HI (United States); University of Hawaii at Manoa
2. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
3. Florida International Univ., Miami, FL (United States); Samara National Research Univ., Samara (Russian Federation)
4. Florida International Univ., Miami, FL (United States)

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

• Research Organization: Univ. of Hawaii at Manoa, Honolulu, HI (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
• Grant/Contract Number: FG02-03ER15411
• OSTI ID: 1603232
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 142; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)Copyright Statement
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY