Infrared absorption of 1-chloro-2-methyl-2-propyl [C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i -C4H8) in solid para -hydrogen

Ching Yin Chou; Yuan-Pern Lee

doi:10.1063/1.4963383

Infrared absorption of 1-chloro-2-methyl-2-propyl [C(CH₃)₂CH₂Cl] and 2-chloro-2-methylpropyl [CH₂C(CH₃)₂Cl] radicals produced in the addition reactions of Cl with isobutene (i -C₄H₈) in solid para -hydrogen

Ching Yin Chou, Yuan-Pern Lee^*

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

The addition reactions of chlorine atom with isobutene (i-C₄H₈) in solid para-hydrogen (p-H₂) were investigated with infrared (IR) absorption spectra. When a p-H₂ matrix containing Cl₂ and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm^-1, and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, C(CH₃)₂CH₂Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm^-1 due to the 2-chloro-2-methylpropyl radical, CH₂C(CH₃)₂Cl, appeared; the ratio of C(CH₃)₂CH₂Cl to CH₂C(CH₃)₂Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H₂ in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H₂ matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C₄H₈Cl₂ and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH₂ClCCl(CH₃)₂, are also characterized.

Original language	English
Article number	134302
Number of pages	13
Journal	Journal of Chemical Physics
Volume	145
Issue number	13
DOIs	https://doi.org/10.1063/1.4963383
State	Published - 7 Oct 2016

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@article{9b73f106bd234b6c924c910f1cb1431b,

title = "Infrared absorption of 1-chloro-2-methyl-2-propyl [C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i -C4H8) in solid para -hydrogen",

abstract = "The addition reactions of chlorine atom with isobutene (i-C4H8) in solid para-hydrogen (p-H2) were investigated with infrared (IR) absorption spectra. When a p-H2 matrix containing Cl2 and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm-1, and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, C(CH3)2CH2Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm-1 due to the 2-chloro-2-methylpropyl radical, CH2C(CH3)2Cl, appeared; the ratio of C(CH3)2CH2Cl to CH2C(CH3)2Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H2 in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H2 matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C4H8Cl2 and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH2ClCCl(CH3)2, are also characterized.",

author = "Chou, {Ching Yin} and Yuan-Pern Lee",

note = "Publisher Copyright: {\textcopyright} 2016 Author(s).",

year = "2016",

month = oct,

day = "7",

doi = "10.1063/1.4963383",

language = "English",

volume = "145",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

number = "13",

}

Infrared absorption of 1-chloro-2-methyl-2-propyl [C(CH₃)₂CH₂Cl] and 2-chloro-2-methylpropyl [CH₂C(CH₃)₂Cl] radicals produced in the addition reactions of Cl with isobutene (i -C₄H₈) in solid para -hydrogen. / Chou, Ching Yin; Lee, Yuan-Pern.
In: Journal of Chemical Physics, Vol. 145, No. 13, 134302, 07.10.2016.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Infrared absorption of 1-chloro-2-methyl-2-propyl [C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i -C4H8) in solid para -hydrogen

AU - Chou, Ching Yin

AU - Lee, Yuan-Pern

PY - 2016/10/7

Y1 - 2016/10/7

N2 - The addition reactions of chlorine atom with isobutene (i-C4H8) in solid para-hydrogen (p-H2) were investigated with infrared (IR) absorption spectra. When a p-H2 matrix containing Cl2 and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm-1, and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, C(CH3)2CH2Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm-1 due to the 2-chloro-2-methylpropyl radical, CH2C(CH3)2Cl, appeared; the ratio of C(CH3)2CH2Cl to CH2C(CH3)2Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H2 in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H2 matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C4H8Cl2 and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH2ClCCl(CH3)2, are also characterized.

AB - The addition reactions of chlorine atom with isobutene (i-C4H8) in solid para-hydrogen (p-H2) were investigated with infrared (IR) absorption spectra. When a p-H2 matrix containing Cl2 and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm-1, and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, C(CH3)2CH2Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm-1 due to the 2-chloro-2-methylpropyl radical, CH2C(CH3)2Cl, appeared; the ratio of C(CH3)2CH2Cl to CH2C(CH3)2Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H2 in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H2 matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C4H8Cl2 and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH2ClCCl(CH3)2, are also characterized.

UR - http://www.scopus.com/inward/record.url?scp=84989945475&partnerID=8YFLogxK

U2 - 10.1063/1.4963383

DO - 10.1063/1.4963383

M3 - Article

AN - SCOPUS:84989945475

SN - 0021-9606

VL - 145

JO - Journal of Chemical Physics

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M1 - 134302