Unconventional Pathway in the Gas‐Phase Synthesis of 9 H ‐Fluorene (C 13 H 10 ) via the Radical–Radical Reaction of Benzyl (C 7 H 7 ) with Phenyl (C 6 H 5 )

He, Chao; Kaiser, Ralf I.; Lu, Wenchao; Ahmed, Musahid; Pivovarov, Pavel S.; Kuznetsov, Oleg V.; Zagidullin, Marsel V.; Mebel, Alexander M.

doi:10.1002/ange.202216972

Unconventional Pathway in the Gas‐Phase Synthesis of 9 H ‐Fluorene (C ₁₃ H ₁₀ ) via the Radical–Radical Reaction of Benzyl (C ₇ H ₇ ) with Phenyl (C ₆ H ₅ )

Journal Article · Sun Jan 08 23:00:00 EST 2023 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202216972· OSTI ID:1908263

He, Chao ^[1]; ^[1]; Lu, Wenchao ^[2]; Ahmed, Musahid ^[2]; Pivovarov, Pavel S. ^[3]; Kuznetsov, Oleg V. ^[3]; Zagidullin, Marsel V. ^[3]; Mebel, Alexander M. ^[4]

Department of Chemistry University of Hawai'i at Mānoa Honolulu HI-96822 USA
Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA-94720 USA
Samara National Research University Samara 443086 Russian Federation
Department of Chemistry and Biochemistry Florida International University Miami FL-33199 USA

Abstract

The simplest polycyclic aromatic hydrocarbon (PAH) carrying a five‐membered ring—9 H ‐fluorene (C ₁₃ H ₁₀ )—is produced isomer‐specifically in the gas phase by reacting benzyl (C ₇ H ₇ ⋅) with phenyl (C ₆ H ₅ ⋅) radicals in a pyrolytic reactor coupled with single photon ionization mass spectrometry. The unconventional mechanism of reaction is supported by theoretical calculations, which first produces diphenylmethane and unexpected 1‐(6‐methylenecyclohexa‐2,4‐dienyl)benzene intermediates (C ₁₃ H ₁₂ ) accessed via addition of the phenyl radical to the ortho position of the benzyl radical. These findings offer convincing evidence for molecular mass growth processes defying conventional wisdom that radical‐radical reactions are initiated through recombination at their radical centers. The structure of 9 H ‐fluorene acts as a molecular building block for complex curved nanostructures like fullerenes and nanobowls providing fundamental insights into the hydrocarbon evolution in high temperature settings.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-03ER15411; FG02-04ER15570; AC02-05CH11231

OSTI ID:: 1908263

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 6 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Unconventional Pathway in the Gas‐Phase Synthesis of 9 H ‐Fluorene (C 13 H 10 ) via the Radical–Radical Reaction of Benzyl (C 7 H 7 ) with Phenyl (C 6 H 5 )

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Unconventional Pathway in the Gas‐Phase Synthesis of 9 H ‐Fluorene (C ₁₃ H ₁₀ ) via the Radical–Radical Reaction of Benzyl (C ₇ H ₇ ) with Phenyl (C ₆ H ₅ )