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A crossed molecular beam and ab-initio investigation of the reaction of boron monoxide (BO; X2Σ+) with methylacetylene (CH3CCH; X1A1): competing atomic hydrogen and methyl loss pathways.
J Phys Chem A. 2013 Nov 21; 117(46):11794-807.JP

Abstract

The gas-phase reaction of boron monoxide ((11)BO; X(2)Σ(+)) with methylacetylene (CH3CCH; X(1)A1) was investigated experimentally using crossed molecular beam technique at a collision energy of 22.7 kJ mol(-1) and theoretically using state of the art electronic structure calculation, for the first time. The scattering dynamics were found to be indirect (complex forming reaction) and the reaction proceeded through the barrier-less formation of a van-der-Waals complex ((11)BOC3H4) followed by isomerization via the addition of (11)BO(X(2)Σ(+)) to the C1 and/or C2 carbon atom of methylacetylene through submerged barriers. The resulting (11)BOC3H4 doublet radical intermediates underwent unimolecular decomposition involving three competing reaction mechanisms via two distinct atomic hydrogen losses and a methyl group elimination. Utilizing partially deuterated methylacetylene reactants (CD3CCH; CH3CCD), we revealed that the initial addition of (11)BO(X(2)Σ(+)) to the C1 carbon atom of methylacetylene was followed by hydrogen loss from the acetylenic carbon atom (C1) and from the methyl group (C3) leading to 1-propynyl boron monoxide (CH3CC(11)BO) and propadienyl boron monoxide (CH2CCH(11)BO), respectively. Addition of (11)BO(X(2)Σ(+)) to the C1 of methylacetylene followed by the migration of the boronyl group to the C2 carbon atom and/or an initial addition of (11)BO(X(2)Σ(+)) to the sterically less accessible C2 carbon atom of methylacetylene was followed by loss of a methyl group leading to the ethynyl boron monoxide product (HCC(11)BO) in an overall exoergic reaction (78 ± 23 kJ mol(-1)). The branching ratios of these channels forming CH2CCH(11)BO, CH3CC(11)BO, and HCC(11)BO were derived to be 4 ± 3%, 40 ± 5%, and 56 ± 15%, respectively; these data are in excellent agreement with the calculated branching ratios using statistical RRKM theory yielding 1%, 38%, and 61%, respectively.

Authors+Show Affiliations

Department of Chemistry, University of Hawai'i at Manoa , Honolulu, Hawaii 96822, United States.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

23651442

Citation

Maity, Surajit, et al. "A Crossed Molecular Beam and Ab-initio Investigation of the Reaction of Boron Monoxide (BO; X2Σ+) With Methylacetylene (CH3CCH; X1A1): Competing Atomic Hydrogen and Methyl Loss Pathways." The Journal of Physical Chemistry. A, vol. 117, no. 46, 2013, pp. 11794-807.
Maity S, Parker DS, Dangi BB, et al. A crossed molecular beam and ab-initio investigation of the reaction of boron monoxide (BO; X2Σ+) with methylacetylene (CH3CCH; X1A1): competing atomic hydrogen and methyl loss pathways. J Phys Chem A. 2013;117(46):11794-807.
Maity, S., Parker, D. S., Dangi, B. B., Kaiser, R. I., Fau, S., Perera, A., & Bartlett, R. J. (2013). A crossed molecular beam and ab-initio investigation of the reaction of boron monoxide (BO; X2Σ+) with methylacetylene (CH3CCH; X1A1): competing atomic hydrogen and methyl loss pathways. The Journal of Physical Chemistry. A, 117(46), 11794-807. https://doi.org/10.1021/jp402743y
Maity S, et al. A Crossed Molecular Beam and Ab-initio Investigation of the Reaction of Boron Monoxide (BO; X2Σ+) With Methylacetylene (CH3CCH; X1A1): Competing Atomic Hydrogen and Methyl Loss Pathways. J Phys Chem A. 2013 Nov 21;117(46):11794-807. PubMed PMID: 23651442.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - A crossed molecular beam and ab-initio investigation of the reaction of boron monoxide (BO; X2Σ+) with methylacetylene (CH3CCH; X1A1): competing atomic hydrogen and methyl loss pathways. AU - Maity,Surajit, AU - Parker,Dorian S N, AU - Dangi,Beni B, AU - Kaiser,Ralf I, AU - Fau,Stefan, AU - Perera,Ajith, AU - Bartlett,Rodney J, Y1 - 2013/05/22/ PY - 2013/5/9/entrez PY - 2013/5/9/pubmed PY - 2013/5/9/medline SP - 11794 EP - 807 JF - The journal of physical chemistry. A JO - J Phys Chem A VL - 117 IS - 46 N2 - The gas-phase reaction of boron monoxide ((11)BO; X(2)Σ(+)) with methylacetylene (CH3CCH; X(1)A1) was investigated experimentally using crossed molecular beam technique at a collision energy of 22.7 kJ mol(-1) and theoretically using state of the art electronic structure calculation, for the first time. The scattering dynamics were found to be indirect (complex forming reaction) and the reaction proceeded through the barrier-less formation of a van-der-Waals complex ((11)BOC3H4) followed by isomerization via the addition of (11)BO(X(2)Σ(+)) to the C1 and/or C2 carbon atom of methylacetylene through submerged barriers. The resulting (11)BOC3H4 doublet radical intermediates underwent unimolecular decomposition involving three competing reaction mechanisms via two distinct atomic hydrogen losses and a methyl group elimination. Utilizing partially deuterated methylacetylene reactants (CD3CCH; CH3CCD), we revealed that the initial addition of (11)BO(X(2)Σ(+)) to the C1 carbon atom of methylacetylene was followed by hydrogen loss from the acetylenic carbon atom (C1) and from the methyl group (C3) leading to 1-propynyl boron monoxide (CH3CC(11)BO) and propadienyl boron monoxide (CH2CCH(11)BO), respectively. Addition of (11)BO(X(2)Σ(+)) to the C1 of methylacetylene followed by the migration of the boronyl group to the C2 carbon atom and/or an initial addition of (11)BO(X(2)Σ(+)) to the sterically less accessible C2 carbon atom of methylacetylene was followed by loss of a methyl group leading to the ethynyl boron monoxide product (HCC(11)BO) in an overall exoergic reaction (78 ± 23 kJ mol(-1)). The branching ratios of these channels forming CH2CCH(11)BO, CH3CC(11)BO, and HCC(11)BO were derived to be 4 ± 3%, 40 ± 5%, and 56 ± 15%, respectively; these data are in excellent agreement with the calculated branching ratios using statistical RRKM theory yielding 1%, 38%, and 61%, respectively. SN - 1520-5215 UR - https://www.unboundmedicine.com/medline/citation/23651442/A_crossed_molecular_beam_and_ab_initio_investigation_of_the_reaction_of_boron_monoxide__BO L2 - https://dx.doi.org/10.1021/jp402743y DB - PRIME DP - Unbound Medicine ER -
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