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Combined Experimental and Computational Study on the Reaction Dynamics of the 1-Propynyl (CH3CC)-1,3-Butadiene (CH2CHCHCH2) System and the Formation of Toluene under Single Collision Conditions.
J Phys Chem A. 2019 May 16; 123(19):4104-4118.JP

Abstract

The crossed beams reactions of the 1-propynyl radical (CH3CC; X2A1) with 1,3-butadiene (CH2CHCHCH2; X1Ag), 1,3-butadiene- d6 (CD2CDCDCD2; X1Ag), 1,3-butadiene- d4 (CD2CHCHCD2; X1Ag), and 1,3-butadiene- d2 (CH2CDCDCH2; X1Ag) were performed under single collision conditions at collision energies of about 40 kJ mol-1. The underlying reaction mechanisms were unraveled through the combination of the experimental data with electronic structure calculations at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) + ZPE(B3LYP/6-311G(d,p) level of theory along with statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations. Together, these data suggest the formation of the thermodynamically most stable C7H8 isomer-toluene (C6H5CH3)-via the barrierless addition of 1-propynyl to the 1,3-butadiene terminal carbon atom, forming a low-lying C7H9 intermediate that undergoes multiple isomerization steps resulting in cyclization and ultimately aromatization following hydrogen atom elimination. RRKM calculations predict that the thermodynamically less stable isomers 1,3-heptadien-5-yne, 5-methylene-1,3-cyclohexadiene, and 3-methylene-1-hexen-4-yne are also synthesized. Since the 1-propynyl radical may be present in cold molecular clouds such as TMC-1, this pathway could potentially serve as a carrier of the methyl group incorporating itself into methyl-substituted (poly)acetylenes or aromatic systems such as toluene via overall exoergic reaction mechanisms that are uninhibited by an entrance barrier. Such pathways are a necessary alternative to existing high energy reactions leading to toluene that are formally closed in the cold regions of space and are an important step toward understanding the synthesis of polycyclic aromatic hydrocarbons (PAHs) in space's harsh extremes.

Authors+Show Affiliations

Department of Chemistry , University of Hawai'i at Manoa , Honolulu , Hawaii 96822 , United States.Department of Chemistry , University of Hawai'i at Manoa , Honolulu , Hawaii 96822 , United States.Department of Chemistry , University of Hawai'i at Manoa , Honolulu , Hawaii 96822 , United States.Department of Chemistry and Biochemistry , Florida International University , Miami , Florida 33199 , United States. Samara National Research University , Samara 443086 , Russia.Department of Chemistry and Biochemistry , Florida International University , Miami , Florida 33199 , United States.Department of Chemistry , University of Hawai'i at Manoa , Honolulu , Hawaii 96822 , United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31017790

Citation

Thomas, Aaron M., et al. "Combined Experimental and Computational Study On the Reaction Dynamics of the 1-Propynyl (CH3CC)-1,3-Butadiene (CH2CHCHCH2) System and the Formation of Toluene Under Single Collision Conditions." The Journal of Physical Chemistry. A, vol. 123, no. 19, 2019, pp. 4104-4118.
Thomas AM, He C, Zhao L, et al. Combined Experimental and Computational Study on the Reaction Dynamics of the 1-Propynyl (CH3CC)-1,3-Butadiene (CH2CHCHCH2) System and the Formation of Toluene under Single Collision Conditions. J Phys Chem A. 2019;123(19):4104-4118.
Thomas, A. M., He, C., Zhao, L., Galimova, G. R., Mebel, A. M., & Kaiser, R. I. (2019). Combined Experimental and Computational Study on the Reaction Dynamics of the 1-Propynyl (CH3CC)-1,3-Butadiene (CH2CHCHCH2) System and the Formation of Toluene under Single Collision Conditions. The Journal of Physical Chemistry. A, 123(19), 4104-4118. https://doi.org/10.1021/acs.jpca.9b00092
Thomas AM, et al. Combined Experimental and Computational Study On the Reaction Dynamics of the 1-Propynyl (CH3CC)-1,3-Butadiene (CH2CHCHCH2) System and the Formation of Toluene Under Single Collision Conditions. J Phys Chem A. 2019 May 16;123(19):4104-4118. PubMed PMID: 31017790.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Combined Experimental and Computational Study on the Reaction Dynamics of the 1-Propynyl (CH3CC)-1,3-Butadiene (CH2CHCHCH2) System and the Formation of Toluene under Single Collision Conditions. AU - Thomas,Aaron M, AU - He,Chao, AU - Zhao,Long, AU - Galimova,Galiya R, AU - Mebel,Alexander M, AU - Kaiser,Ralf I, Y1 - 2019/05/07/ PY - 2019/4/25/pubmed PY - 2019/4/25/medline PY - 2019/4/25/entrez SP - 4104 EP - 4118 JF - The journal of physical chemistry. A JO - J Phys Chem A VL - 123 IS - 19 N2 - The crossed beams reactions of the 1-propynyl radical (CH3CC; X2A1) with 1,3-butadiene (CH2CHCHCH2; X1Ag), 1,3-butadiene- d6 (CD2CDCDCD2; X1Ag), 1,3-butadiene- d4 (CD2CHCHCD2; X1Ag), and 1,3-butadiene- d2 (CH2CDCDCH2; X1Ag) were performed under single collision conditions at collision energies of about 40 kJ mol-1. The underlying reaction mechanisms were unraveled through the combination of the experimental data with electronic structure calculations at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) + ZPE(B3LYP/6-311G(d,p) level of theory along with statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations. Together, these data suggest the formation of the thermodynamically most stable C7H8 isomer-toluene (C6H5CH3)-via the barrierless addition of 1-propynyl to the 1,3-butadiene terminal carbon atom, forming a low-lying C7H9 intermediate that undergoes multiple isomerization steps resulting in cyclization and ultimately aromatization following hydrogen atom elimination. RRKM calculations predict that the thermodynamically less stable isomers 1,3-heptadien-5-yne, 5-methylene-1,3-cyclohexadiene, and 3-methylene-1-hexen-4-yne are also synthesized. Since the 1-propynyl radical may be present in cold molecular clouds such as TMC-1, this pathway could potentially serve as a carrier of the methyl group incorporating itself into methyl-substituted (poly)acetylenes or aromatic systems such as toluene via overall exoergic reaction mechanisms that are uninhibited by an entrance barrier. Such pathways are a necessary alternative to existing high energy reactions leading to toluene that are formally closed in the cold regions of space and are an important step toward understanding the synthesis of polycyclic aromatic hydrocarbons (PAHs) in space's harsh extremes. SN - 1520-5215 UR - https://www.unboundmedicine.com/medline/citation/31017790/Combined_Experimental_and_Computational_Study_on_the_Reaction_Dynamics_of_the_1_Propynyl__CH3CC__13_Butadiene__CH2CHCHCH2__System_and_the_Formation_of_Toluene_under_Single_Collision_Conditions_ L2 - https://dx.doi.org/10.1021/acs.jpca.9b00092 DB - PRIME DP - Unbound Medicine ER -
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