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A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X(2)Π) with Methylacetylene (CH3CCH; X(1)A1) and D4-Methylacetylene (CD3CCD; X(1)A1).
J Phys Chem A. 2016 Jul 14; 120(27):4872-83.JP

Abstract

The bimolecular gas-phase reactions of the ground-state silylidyne radical (SiH; X(2)Π) with methylacetylene (CH3CCH; X(1)A1) and D4-methylacetylene (CD3CCD; X(1)A1) were explored at collision energies of 30 kJ mol(-1) under single-collision conditions exploiting the crossed molecular beam technique and complemented by electronic structure calculations. These studies reveal that the reactions follow indirect scattering dynamics, have no entrance barriers, and are initiated by the addition of the silylidyne radical to the carbon-carbon triple bond of the methylacetylene molecule either to one carbon atom (C1; [i1]/[i2]) or to both carbon atoms concurrently (C1-C2; [i3]). The collision complexes [i1]/[i2] eventually isomerize via ring-closure to the c-SiC3H5 doublet radical intermediate [i3], which is identified as the decomposing reaction intermediate. The hydrogen atom is emitted almost perpendicularly to the rotational plane of the fragmenting complex resulting in a sideways scattering dynamics with the reaction being overall exoergic by -12 ± 11 kJ mol(-1) (experimental) and -1 ± 3 kJ mol(-1) (computational) to form the cyclic 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC3H4; p1). In line with computational data, experiments of silylidyne with D4-methylacetylene (CD3CCD; X(1)A1) depict that the hydrogen is emitted solely from the silylidyne moiety but not from methylacetylene. The dynamics are compared to those of the related D1-silylidyne (SiD; X(2)Π)-acetylene (HCCH; X(1)Σg(+)) reaction studied previously in our group, and from there, we discovered that the methyl group acts primarily as a spectator in the title reaction. The formation of 2-methyl-1-silacycloprop-2-enylidene under single-collision conditions via a bimolecular gas-phase reaction augments our knowledge of the hitherto poorly understood silylidyne (SiH; X(2)Π) radical reactions with small hydrocarbon molecules leading to the synthesis of organosilicon molecules in cold molecular clouds and in carbon-rich circumstellar envelopes.

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, University of California, Berkeley , Berkeley, California 94720, United States.Department of Chemistry, University of California, Berkeley , Berkeley, California 94720, United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

26837568

Citation

Yang, Tao, et al. "A Combined Experimental and Theoretical Study On the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule Via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X(2)Π) With Methylacetylene (CH3CCH; X(1)A1) and D4-Methylacetylene (CD3CCD; X(1)A1)." The Journal of Physical Chemistry. A, vol. 120, no. 27, 2016, pp. 4872-83.
Yang T, Dangi BB, Kaiser RI, et al. A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X(2)Π) with Methylacetylene (CH3CCH; X(1)A1) and D4-Methylacetylene (CD3CCD; X(1)A1). J Phys Chem A. 2016;120(27):4872-83.
Yang, T., Dangi, B. B., Kaiser, R. I., Bertels, L. W., & Head-Gordon, M. (2016). A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X(2)Π) with Methylacetylene (CH3CCH; X(1)A1) and D4-Methylacetylene (CD3CCD; X(1)A1). The Journal of Physical Chemistry. A, 120(27), 4872-83. https://doi.org/10.1021/acs.jpca.5b12457
Yang T, et al. A Combined Experimental and Theoretical Study On the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule Via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X(2)Π) With Methylacetylene (CH3CCH; X(1)A1) and D4-Methylacetylene (CD3CCD; X(1)A1). J Phys Chem A. 2016 Jul 14;120(27):4872-83. PubMed PMID: 26837568.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X(2)Π) with Methylacetylene (CH3CCH; X(1)A1) and D4-Methylacetylene (CD3CCD; X(1)A1). AU - Yang,Tao, AU - Dangi,Beni B, AU - Kaiser,Ralf I, AU - Bertels,Luke W, AU - Head-Gordon,Martin, Y1 - 2016/02/19/ PY - 2016/2/4/entrez PY - 2016/2/4/pubmed PY - 2016/2/4/medline SP - 4872 EP - 83 JF - The journal of physical chemistry. A JO - J Phys Chem A VL - 120 IS - 27 N2 - The bimolecular gas-phase reactions of the ground-state silylidyne radical (SiH; X(2)Π) with methylacetylene (CH3CCH; X(1)A1) and D4-methylacetylene (CD3CCD; X(1)A1) were explored at collision energies of 30 kJ mol(-1) under single-collision conditions exploiting the crossed molecular beam technique and complemented by electronic structure calculations. These studies reveal that the reactions follow indirect scattering dynamics, have no entrance barriers, and are initiated by the addition of the silylidyne radical to the carbon-carbon triple bond of the methylacetylene molecule either to one carbon atom (C1; [i1]/[i2]) or to both carbon atoms concurrently (C1-C2; [i3]). The collision complexes [i1]/[i2] eventually isomerize via ring-closure to the c-SiC3H5 doublet radical intermediate [i3], which is identified as the decomposing reaction intermediate. The hydrogen atom is emitted almost perpendicularly to the rotational plane of the fragmenting complex resulting in a sideways scattering dynamics with the reaction being overall exoergic by -12 ± 11 kJ mol(-1) (experimental) and -1 ± 3 kJ mol(-1) (computational) to form the cyclic 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC3H4; p1). In line with computational data, experiments of silylidyne with D4-methylacetylene (CD3CCD; X(1)A1) depict that the hydrogen is emitted solely from the silylidyne moiety but not from methylacetylene. The dynamics are compared to those of the related D1-silylidyne (SiD; X(2)Π)-acetylene (HCCH; X(1)Σg(+)) reaction studied previously in our group, and from there, we discovered that the methyl group acts primarily as a spectator in the title reaction. The formation of 2-methyl-1-silacycloprop-2-enylidene under single-collision conditions via a bimolecular gas-phase reaction augments our knowledge of the hitherto poorly understood silylidyne (SiH; X(2)Π) radical reactions with small hydrocarbon molecules leading to the synthesis of organosilicon molecules in cold molecular clouds and in carbon-rich circumstellar envelopes. SN - 1520-5215 UR - https://www.unboundmedicine.com/medline/citation/26837568/A_Combined_Experimental_and_Theoretical_Study_on_the_Formation_of_the_2_Methyl_1_silacycloprop_2_enylidene_Molecule_via_the_Crossed_Beam_Reactions_of_the_Silylidyne_Radical__SiH L2 - https://dx.doi.org/10.1021/acs.jpca.5b12457 DB - PRIME DP - Unbound Medicine ER -
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