Reaction dynamics of the 4-methylphenyl radical (C6H4CH3; p-tolyl) with isoprene (C5H8) – formation of dimethyldihydronaphthalenes

Dangi, Beni B.; Yang, Tao; Kaiser, Ralf I.; Mebel, Alexander M.

doi:10.1039/c4cp01056f

Reaction dynamics of the 4-methylphenyl radical (C₆H₄CH₃; p-tolyl) with isoprene (C₅H₈) – formation of dimethyldihydronaphthalenes

Journal Article · Fri Jun 27 00:00:00 EDT 2014 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c4cp01056f· OSTI ID:1602787

Dangi, Beni B. ^[1]; Yang, Tao ^[2]; Kaiser, Ralf I. ^[2]; Mebel, Alexander M. ^[3]

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

We probed the reaction of the 4-methylphenyl radical with isoprene under single collision conditions at a collision energy of 58 kJ mol^-1 by exploiting the crossed molecular beam technique. Supported by the electronic structure calculations, the reaction was found to initially lead to a van-der-Waals complex without any barrier which can then isomerize by addition of the 4-methylphenyl radical to any one of the four carbon atoms of the 1,3-butadiene moiety of isoprene. The initial addition products isomerize with formal addition products preferentially to C1 and C4 carbon atoms of the isoprene. These structures further isomerize via hydrogen migration and cyclization; the reaction is terminated by a hydrogen atom elimination from the 4-methylphenyl moiety via tight exit transition states leading to two dimethyl-dihydronaphthalene isomers as the dominating products. Here, this study presents one of the very first bimolecular reactions of the 4-methylphenyl radical with unsaturated hydrocarbons and opens a path for the investigation of this reaction class in future experiments.

View Accepted Manuscript (DOE)

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; FG02-04ER15570

OSTI ID:: 1602787

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 31 Vol. 16; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Indene Formation under Single-Collision Conditions from the Reaction of Phenyl Radicals with Allene and Methylacetylene-A Crossed Molecular Beam and Ab Initio Study Parker, Dr Dorian S. N.; Zhang, Dr Fangtong; Kaiser, Dr Ralf I. Chemistry - An Asian Journal, Vol. 6, Issue 11 https://doi.org/10.1002/asia.201100535	journal	September 2011
The high temperature oxidation of the methyl side chain of toluene Brezinsky, K.; Litzinger, T. A.; Glassman, I. International Journal of Chemical Kinetics, Vol. 16, Issue 9 https://doi.org/10.1002/kin.550160902	journal	September 1984
Rate constants for the reactions of benzyl and methyl-substituted benzyl radicals with O2 and NO Ebata, Takayuki; Obi, Kin-ichi; Tanaka, Ikuzo Chemical Physics Letters, Vol. 77, Issue 3 https://doi.org/10.1016/0009-2614(81)85190-1	journal	February 1981
Three dissociation channels for p-dichlorobenzene excited at 193 nm in molecular beams Ichimura, Teijiro; Mori, Yuji; Shinohara, Hisanori Chemical Physics Letters, Vol. 122, Issue 1-2 https://doi.org/10.1016/0009-2614(85)85477-4	journal	November 1985
The surface structure and reactivity of black carbon Smith, D. M.; Chughtai, A. R. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 105, Issue 1 https://doi.org/10.1016/0927-7757(95)03337-1	journal	December 1995
The oxidation of soot: a review of experiments, mechanisms and models Stanmore, B. R.; Brilhac, J. F.; Gilot, P. Carbon, Vol. 39, Issue 15 https://doi.org/10.1016/S0008-6223(01)00109-9	journal	December 2001
Gaussian-3 theory using coupled cluster energies Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C. Chemical Physics Letters, Vol. 314, Issue 1-2 https://doi.org/10.1016/S0009-2614(99)01126-4	journal	November 1999
On the relative contribution of acetylene and aromatics to soot particle surface growth Kazakov, Andrei; Frenklach, Michael Combustion and Flame, Vol. 112, Issue 1-2 https://doi.org/10.1016/S0010-2180(97)81776-2	journal	January 1998
Analysis of real-time variables affecting children's exposure to diesel-related pollutants during school bus commutes in Los Angeles Sabin, Lisa D.; Kozawa, Kathleen; Behrentz, Eduardo Atmospheric Environment, Vol. 39, Issue 29 https://doi.org/10.1016/j.atmosenv.2005.05.037	journal	September 2005
PAH Growth from the pyrolysis of CPD, indene and naphthalene mixture Lu, Mingming; Mulholland, James A. Chemosphere, Vol. 55, Issue 4 https://doi.org/10.1016/j.chemosphere.2003.12.002	journal	April 2004
An experimental and theoretical study of toluene pyrolysis with tunable synchrotron VUV photoionization and molecular-beam mass spectrometry Zhang, Taichang; Zhang, Lidong; Hong, Xin Combustion and Flame, Vol. 156, Issue 11 https://doi.org/10.1016/j.combustflame.2009.06.001	journal	November 2009
Isomerization kinetics of benzylic and methylphenyl type radicals in single-ring aromatics Dames, Enoch; Wang, Hai Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.05.014	journal	January 2013
Molecular Reaction Dynamics Levine, Raphael D. https://doi.org/10.1017/CBO9780511614125	book	January 2005
Human Cell Mutagens in Respirable Airborne Particles from the Northeastern United States. 2. Quantification of Mutagens and Other Organic Compounds Pedersen, Daniel U.; Durant, John L.; Taghizadeh, Koli Environmental Science & Technology, Vol. 39, Issue 24 https://doi.org/10.1021/es050886c	journal	December 2005
Pulse radiolysis, flash-photolysis, and shock wave study of the recombination hydrogen atom + benzyl .fwdarw. toluene at 300 and 1300-1650 K Ackermann, L.; Hippler, H.; Pagsberg, P. The Journal of Physical Chemistry, Vol. 94, Issue 13 https://doi.org/10.1021/j100376a015	journal	June 1990
Carbon-carbon and carbon-hydrogen bond splits of laser-excited aromatic molecules. 1. Specific and thermally averaged rate constants Brand, U.; Hippler, H.; Lindemann, L. The Journal of Physical Chemistry, Vol. 94, Issue 16 https://doi.org/10.1021/j100379a030	journal	August 1990
Reaction of the benzyl radical with oxygen and chlorine Nelson, H. H.; McDonald, J. R. The Journal of Physical Chemistry, Vol. 86, Issue 8 https://doi.org/10.1021/j100397a004	journal	April 1982
A direct mass spectrometric study of the mechanism of toluene pyrolysis at high temperatures Smith, Richard D. The Journal of Physical Chemistry, Vol. 83, Issue 12 https://doi.org/10.1021/j100475a001	journal	June 1979
Absolute rate constants for metathesis reactions of allyl and benzyl radicals with hydriodic acid (hydriodic acid-d). Heat of formation of allyl and benzyl radicals Rossi, M.; Golden, D. M. Journal of the American Chemical Society, Vol. 101, Issue 5 https://doi.org/10.1021/ja00499a030	journal	February 1979
Adsorption of Gas-Phase Nitric Acid to n -Hexane Soot: Thermodynamics and Mechanism Aubin, Daniel G.; Abbatt, Jonathan P. The Journal of Physical Chemistry A, Vol. 107, Issue 50 https://doi.org/10.1021/jp036105g	journal	December 2003
Identification of C ₅ H _x Isomers in Fuel-Rich Flames by Photoionization Mass Spectrometry and Electronic Structure Calculations Hansen, Nils; Klippenstein, Stephen J.; Miller, James A. The Journal of Physical Chemistry A, Vol. 110, Issue 13 https://doi.org/10.1021/jp0569685	journal	April 2006
On the Combination Reactions of Hydrogen Atoms with Resonance-Stabilized Hydrocarbon Radicals ^† Harding, Lawrence B.; Klippenstein, Stephen J.; Georgievskii, Yuri The Journal of Physical Chemistry A, Vol. 111, Issue 19 https://doi.org/10.1021/jp0682309	journal	May 2007
Toluene Combustion: Reaction Paths, Thermochemical Properties, and Kinetic Analysis for the Methylphenyl Radical + O ₂ Reaction da Silva, Gabriel; Chen, Chiung-Chu; Bozzelli, Joseph W. The Journal of Physical Chemistry A, Vol. 111, Issue 35 https://doi.org/10.1021/jp068640x	journal	September 2007
PAH Formation under Single Collision Conditions: Reaction of Phenyl Radical and 1,3-Butadiene to Form 1,4-Dihydronaphthalene Kaiser, R. I.; Parker, D. S. N.; Zhang, F. The Journal of Physical Chemistry A, Vol. 116, Issue 17 https://doi.org/10.1021/jp301775z	journal	April 2012
Role of Phenyl Radicals in the Growth of Polycyclic Aromatic Hydrocarbons Shukla, Bikau; Susa, Akio; Miyoshi, Akira The Journal of Physical Chemistry A, Vol. 112, Issue 11 https://doi.org/10.1021/jp7098398	journal	March 2008
Kinetics of the Cyclopentadienyl + Acetylene, Fulvenallene + H, and 1-Ethynylcyclopentadiene + H Reactions da Silva, Gabriel; Cole, John A.; Bozzelli, Joseph W. The Journal of Physical Chemistry A, Vol. 114, Issue 6 https://doi.org/10.1021/jp906835w	journal	February 2010
Photochemical Effects in the Heterogeneous Reaction of Soot with Ozone at Low Concentrations Smith, D. M.; Chughtai, A. R. Journal of Atmospheric Chemistry, Vol. 26, Issue 1, p. 77-91 https://doi.org/10.1023/A:1005702818675	journal	January 1997
Residential environmental exposures and other characteristics associated with detectable PAH-DNA adducts in peripheral mononuclear cells in a population-based sample of adult females Shantakumar, Sumitra; Gammon, Marilie D.; Eng, Sybil M. Journal of Exposure Science & Environmental Epidemiology, Vol. 15, Issue 6 https://doi.org/10.1038/sj.jea.7500426	journal	April 2005
Reaction mechanism of soot formation in flames Frenklach, Michael Physical Chemistry Chemical Physics, Vol. 4, Issue 11 https://doi.org/10.1039/b110045a	journal	February 2002
Untangling the chemical evolution of Titan's atmosphere and surface–from homogeneous to heterogeneous chemistry Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney Faraday Discussions, Vol. 147 https://doi.org/10.1039/c003599h	journal	January 2010
Exchange reactions of alkali atoms with alkali halides: a collision complex mechanism Miller, W. B.; Safron, S. A.; Herschbach, D. R. Discussions of the Faraday Society, Vol. 44 https://doi.org/10.1039/df9674400108	journal	January 1967
The inner wind of IRC+10216 revisited: new exotic chemistry and diagnostic for dust condensation in carbon stars Cherchneff, I. Astronomy & Astrophysics, Vol. 545 https://doi.org/10.1051/0004-6361/201118542	journal	August 2012
Reactivity of Methyl and Tolyl Radicals from Xylene Pyrolysis Burr, J. G.; Strong, J. D. The Journal of Chemical Physics, Vol. 43, Issue 4 https://doi.org/10.1063/1.1696946	journal	August 1965
Scintillation Type Mass Spectrometer Ion Detector Daly, N. R. Review of Scientific Instruments, Vol. 31, Issue 3 https://doi.org/10.1063/1.1716953	journal	March 1960
Design of a modular and versatile interlock system for ultrahigh vacuum machines: A crossed molecular beam setup as a case study Guo, Ying; Gu, Xibin; Kawamura, Ed Review of Scientific Instruments, Vol. 77, Issue 3 https://doi.org/10.1063/1.2173074	journal	March 2006
Intramolecular hydrogen transfer in the o ‐tolyl radical studied by time resolved absorption measurements Ichimura, Teijiro; Mori, Yuji; Sumitani, Minoru The Journal of Chemical Physics, Vol. 84, Issue 3 https://doi.org/10.1063/1.450448	journal	February 1986
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Photofragmentation of chlorotoluenes and dichlorobenzenes: Substituent effects on the dissociation mechanism, and angular distribution of the Cl fragment Ichimura, Teijiro; Mori, Yuji; Shinohara, Hisanori The Journal of Chemical Physics, Vol. 107, Issue 3 https://doi.org/10.1063/1.474383	journal	July 1997
Gaussian-3 (G3) theory for molecules containing first and second-row atoms Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C. The Journal of Chemical Physics, Vol. 109, Issue 18 https://doi.org/10.1063/1.477422	journal	November 1998
Gaussian-3 theory using density functional geometries and zero-point energies Baboul, Anwar G.; Curtiss, Larry A.; Redfern, Paul C. The Journal of Chemical Physics, Vol. 110, Issue 16 https://doi.org/10.1063/1.478676	journal	April 1999
Low temperature formation of naphthalene and its role in the synthesis of PAHs (Polycyclic Aromatic Hydrocarbons) in the interstellar medium Parker, D. S. N.; Zhang, F.; Kim, Y. S. Proceedings of the National Academy of Sciences, Vol. 109, Issue 1 https://doi.org/10.1073/pnas.1113827108	journal	December 2011
The Identification of Cyclopenta-Fused and Ethynyl-Substituted Polycyclic Aromatic Hydrocarbons in Benzene Droplet Combustion Products Marsh, Nathan D.; Wornat, Mary J.; Scott, Lawrence T. Polycyclic Aromatic Compounds, Vol. 13, Issue 4 https://doi.org/10.1080/10406630008233852	journal	April 2000
Influence of Soil Fertilization by Sewage Sludge on the Content of Polycyclic Aromatic Hydrocarbons (PAHs) in Crops Oleszczuk, Patryk; Baran, StanisŁAw Journal of Environmental Science and Health, Part A, Vol. 40, Issue 11 https://doi.org/10.1080/10934520500232712	journal	November 2005
Polycyclic Aromatic Hydrocarbon (PAH) Ecotoxicology in Marine Ecosystems Hylland, Ketil Journal of Toxicology and Environmental Health, Part A, Vol. 69, Issue 1-2 https://doi.org/10.1080/15287390500259327	journal	January 2006
Modeling the Unidentified Infrared Emission with Combinations of Polycyclic Aromatic Hydrocarbons Allamandola, L. J.; Hudgins, D. M.; Sandford, S. A. The Astrophysical Journal, Vol. 511, Issue 2 https://doi.org/10.1086/311843	journal	February 1999
Chromium(VI) exposure enhances polycyclic aromatic hydrocarbon-DNA binding at the p53 gene in human lung cells Feng, Z. Carcinogenesis, Vol. 24, Issue 4 https://doi.org/10.1093/carcin/bgg012	journal	April 2003
Long-Term Effects of a Standardized Complex Mixture of Urban Dust Particulate on the Metabolic Activation of Carcinogenic Polycyclic Aromatic Hydrocarbons in Human Cells in Culture Musafia-Jeknic, Tamara; Mahadevan, Brinda; Pereira, Clifford Toxicological Sciences, Vol. 88, Issue 2 https://doi.org/10.1093/toxsci/kfi329	journal	September 2005
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Molecular Diffuse Interstellar Band Carriers in the Red Rectangle Sarre, P. J.; Miles, J. R.; Scarrott, S. M. Science, Vol. 269, Issue 5224 https://doi.org/10.1126/science.269.5224.674	journal	August 1995
Tropospheric Air Pollution: Ozone, Airborne Toxics, Polycyclic Aromatic Hydrocarbons, and Particles Finlayson-Pitts, B. J. Science, Vol. 276, Issue 5315 https://doi.org/10.1126/science.276.5315.1045	journal	May 1997
Kinetics of the recombination of methyl radicals with benzyl radicals Kominar, R. J.; Jacko, M. G.; Price, S. J. Canadian Journal of Chemistry, Vol. 45, Issue 6 https://doi.org/10.1139/v67-095	journal	March 1967
Interstellar Polycyclic Aromatic Hydrocarbon Molecules Tielens, A. G. G. M. Annual Review of Astronomy and Astrophysics, Vol. 46, Issue 1 https://doi.org/10.1146/annurev.astro.46.060407.145211	journal	September 2008
O RGANIC A TMOSPHERIC P ARTICULATE M ATERIAL Seinfeld, John H.; Pankow, James F. Annual Review of Physical Chemistry, Vol. 54, Issue 1 https://doi.org/10.1146/annurev.physchem.54.011002.103756	journal	October 2003
Formation of C ₆ H ₆ Isomers by Recombination of Propynyl in the System Sodium Vapour/Propynylhalide Alkemade, U.; Homann, K. H. Zeitschrift für Physikalische Chemie, Vol. 161, Issue Part_1_2 https://doi.org/10.1524/zpch.1989.161.Part_1_2.019	journal	January 1989

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