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The Hidden Path to the Resonance-Stabilized Fulvenallenyl Radical (C7H5) via the Bimolecular Reaction of Tricarbon (C3, X1Σg+) with 1,3-Butadiene (C4H6; X1Ag)

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [3];  [1];  [1];  [1]
  1. University of Hawaii at Manoa, Honolulu, HI (United States)
  2. Florida International University, Miami, FL (United States)
  3. Samara National Research University (Russia)
+ Show Author Affiliations
Here, we report a novel bimolecular reaction pathway forming the resonance-stabilized fulvenallenyl radical (C7H5) via the gas-phase reaction of tricarbon (C3, X1Σg+) with 1,3-butadiene (C4H6, X1Ag). Crossed molecular beam experiments combined with high-level electronic structures and statistical calculations reveal a rich potential energy surface. The reaction proceeds via tricarbon addition to a double bond of 1,3-butadiene, overcoming a 30 kJ mol–1 barrier, followed by ring closure, isomerizations (ring opening/closures, hydrogen shifts), and eventual hydrogen atom loss, yielding the fulvenallenyl radical (p1) almost exclusively via two dominant pathways. Considering the entrance barrier, this reaction may occur in high-temperature environments, like circumstellar envelopes of carbon stars, but is suppressed in colder regions such as molecular clouds and Titan’s atmosphere. These findings highlight the unexpected reactivity of small carbon clusters in shaping the molecular complexity of our universe, from the flicker of a flame to the death of a star.
Research Organization:
Florida International University, Miami, FL (United States); University of Hawaii at Manoa, Honolulu, HI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-03ER15411
OSTI ID:
3023804
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 10 Vol. 17; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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