Formation of 2- and 1-methyl-1,4-dihydronaphthalene isomers via the crossed beam reactions of phenyl radicals (C6H5) with isoprene (CH2C(CH3)CHCH 2) and 1,3-pentadiene (CH2CHCHCHCH3)

Yang, Tao; Muzangwa, Lloyd; Parker, Dorian S.  N.; Kaiser, Ralf I.; Mebel, Alexander M.

doi:10.1039/c4cp04612a

Formation of 2- and 1-methyl-1,4-dihydronaphthalene isomers via the crossed beam reactions of phenyl radicals (C₆H₅) with isoprene (CH₂C(CH₃)CHCH ₂) and 1,3-pentadiene (CH₂CHCHCHCH₃)

Journal Article · Fri Nov 07 04:00:00 EST 2014 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c4cp04612a· OSTI ID:1602875

Yang, Tao ^[1]; Muzangwa, Lloyd ^[2]; Parker, Dorian S. N. ^[2]; Kaiser, Ralf I. ^[2]; Mebel, Alexander M. ^[3]

Univ. of Hawaii at Manoa, Honolulu, HI (United States); University of Hawaii at Manoa
Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Florida International Univ., Miami, FL (United States)

Crossed molecular beam reactions were exploited to elucidate the chemical dynamics of the reactions of phenyl radicals with isoprene and with 1,3-pentadiene at a collision energy of 55 ± 4 kJ mol^-1. Both reactions were found to proceed via indirect scattering dynamics and involve the formation of a van-der-Waals complex in the entrance channel. The latter isomerized via the addition of the phenyl radical to the terminal C1/C4 carbon atoms through submerged barriers forming resonantly stabilized free radicals C₁₁H₁₃, which then underwent cis–trans isomerization followed by ring closure. The resulting bicyclic intermediates fragmented via unimolecular decomposition though the atomic hydrogen loss via tight exit transition states located 30 kJ mol^-1 above the separated reactants in overall exoergic reactions forming 2- and 1-methyl-1,4-dihydronaphthalene isomers. The hydrogen atoms are emitted almost perpendicularly to the plane of the decomposing complex and almost parallel to the total angular momentum vector (‘sideways scattering’) which is in strong analogy to the phenyl–1,3-butadiene system studied earlier. RRKM calculations confirm that 2- and 1-methyl-1,4-dihydronaphthalene are the dominating reaction products formed at levels of 97% and 80% in the reactions of the phenyl radical with isoprene and 1,3-pentadiene, respectively. This barrier-less formation of methyl-substituted, hydrogenated PAH molecules further supports our understanding of the formation of aromatic molecules in extreme environments holding temperatures as low as 10 K.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Hawaii at Manoa, Honolulu, HI (United States); Florida International Univ., Miami, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

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

OSTI ID:: 1602875

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 1 Vol. 17; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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