Journal of the Chemical Society Perkin Transactions 2, volume 2, issue 3, pages 687-699

EPR study of methyl and ethyl acrylate radical cations and their transformations in low-temperature matrices

Knolle W. ¹

Feldman Vladimir I. ^{2, 3}

Janovský Igor ¹

Naumov Sergej ¹

Mehnert Reiner ¹

Langguth Helmut ¹

Sukhov Fedor F ³

Orlov Aleksei Yu ²

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Institut für Oberflächenmodifizierung (IOM), Permoserstr.15, D-04303 Leipzig, Germany |

Institute of Synthetic Polymeric Materials of RAS, Profsojuznaya Str. 70, 117393 Moscow, Russia |

Karpov Institute of Physical Chemistry, Vorontsovo pole Str. 10, 103064 Moscow, Russia |

Publication type: Journal Article

Publication date: 2002-02-11

Royal Society of Chemistry (RSC)

Journal: Journal of the Chemical Society Perkin Transactions 2

Quartile SCImago

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Quartile WOS

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Impact factor: —

ISSN: 03009580, 13645471

DOI: 10.1039/b105384c

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General Environmental Science

General Earth and Planetary Sciences

Abstract

Using low-temperature EPR spectroscopy, transformations of radical cations of methyl (MeA) and ethyl acrylate (EtA) radiolytically generated in freon (CFCl2CF2Cl, CF3CCl3 and CFCl3) and in argon matrices were investigated. The assignment of the EPR spectra was made with the help of partially deuterated acrylates, namely ethyl-d2 (EtA-d2) and ethyl-d5 acrylates (EtA-d5) and methyl-d3 acrylate (MeA-d3). In addition, quantum chemical calculations were performed to obtain information on the electronic structure, the hfs constants and energy levels of the transient species observed. The primary radical cations show broad singlet spectra (ΔHpp ≈ 1.4 mT) and transform quickly by hydrogen transfer from the ester group to the carbonyl oxygen leading to distonic radical cations. This transformation can be observed directly at 77 K in the case of the MeA leading to CH2CH–(COH)+–OCH2˙ (a(2Hα) = 2.24 mT, first-order rate constant in CF3CCl3: 1 h−1). The primary cation of EtA could be trapped below 40 K in a CFCl3 matrix only. In all the freon matrices studied, the intramolecular rearrangement of this cation yields the CH2CH–(COH)+–OCH2CH2˙ terminal-type distonic radical cation. The conformation of the latter species in polycrystalline CFCl3 and CF3CCl3 matrices corresponds to the calculated minimum close to the transition state geometry. In the case of CF3CCl3 matrix, warming the samples to temperatures above 130 K results in the simultaneous formation of two new species, which were assigned to six- and five-member ring structures (a(H)/mT: 2.36 (Hα), 5.13 (Hβ1), 1.9 (Hβ2) and 2.27 (2Hα), 2.6 (Hβ), respectively) formed by intramolecular cycloaddition of the terminal radical to the vinyl double bond. The formation of the propagating radical –CH2–CH˙–R due to an ion-molecule reaction is observed in CFCl2CF2Cl at temperatures above 98 K; this process was also detected in other freons under the conditions of matrix softening. The primary radical cation of EtA is not trapped in an argon matrix even at 16 K due to the realisation of the “high-energy” reaction paths yielding methyl radicals and, probably, rearrangement products.

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Citations by journals

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Radiation Physics and Chemistry	Radiation Physics and Chemistry, 6, 31.58% Radiation Physics and Chemistry 6 publications, 31.58%
Journal of Physical Chemistry A	Journal of Physical Chemistry A, 2, 10.53% Journal of Physical Chemistry A 2 publications, 10.53%
Nuclear Instruments and Methods in Physics Research, Section B: Beam Interactions with Materials and Atoms	Nuclear Instruments and Methods in Physics Research, Section B: Beam Interactions with Materials and Atoms, 2, 10.53% Nuclear Instruments and Methods in Physics Research, Section B: Beam Interactions with Materials and Atoms 2 publications, 10.53%
Vibronic Interactions and the Jahn-Teller Effect	Vibronic Interactions and the Jahn-Teller Effect, 1, 5.26% Vibronic Interactions and the Jahn-Teller Effect 1 publication, 5.26%
Journal of Molecular Structure	Journal of Molecular Structure, 1, 5.26% Journal of Molecular Structure 1 publication, 5.26%
Nanomaterials	Nanomaterials, 1, 5.26% Nanomaterials 1 publication, 5.26%
Chemistry - A European Journal	Chemistry - A European Journal, 1, 5.26% Chemistry - A European Journal 1 publication, 5.26%
Polymer International	Polymer International, 1, 5.26% Polymer International 1 publication, 5.26%
Physical Chemistry Chemical Physics	Physical Chemistry Chemical Physics, 1, 5.26% Physical Chemistry Chemical Physics 1 publication, 5.26%
Asymmetric Top Molecules. Part 2	Asymmetric Top Molecules. Part 2, 1, 5.26% Asymmetric Top Molecules. Part 2 1 publication, 5.26%
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Citations by publishers

	1 2 3 4 5 6 7 8 9
Elsevier	Elsevier, 9, 47.37% Elsevier 9 publications, 47.37%
American Chemical Society (ACS)	American Chemical Society (ACS), 2, 10.53% American Chemical Society (ACS) 2 publications, 10.53%
Springer Nature	Springer Nature, 2, 10.53% Springer Nature 2 publications, 10.53%
Wiley	Wiley, 2, 10.53% Wiley 2 publications, 10.53%
Multidisciplinary Digital Publishing Institute (MDPI)	Multidisciplinary Digital Publishing Institute (MDPI), 1, 5.26% Multidisciplinary Digital Publishing Institute (MDPI) 1 publication, 5.26%
Royal Society of Chemistry (RSC)	Royal Society of Chemistry (RSC), 1, 5.26% Royal Society of Chemistry (RSC) 1 publication, 5.26%
	1 2 3 4 5 6 7 8 9

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Knolle W. et al. EPR study of methyl and ethyl acrylate radical cations and their transformations in low-temperature matrices // Journal of the Chemical Society Perkin Transactions 2. 2002. Vol. 2. No. 3. pp. 687-699.

GOST all authors (up to 50) Copy

Knolle W., Feldman V. I., Janovský I., Naumov S., Mehnert R., Langguth H., Sukhov F. F., Orlov A. Yu. EPR study of methyl and ethyl acrylate radical cations and their transformations in low-temperature matrices // Journal of the Chemical Society Perkin Transactions 2. 2002. Vol. 2. No. 3. pp. 687-699.

RIS |

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RIS Copy

TY - JOUR

DO - 10.1039/b105384c

UR - https://doi.org/10.1039%2Fb105384c

TI - EPR study of methyl and ethyl acrylate radical cations and their transformations in low-temperature matrices

T2 - Journal of the Chemical Society Perkin Transactions 2

AU - Janovský, Igor

AU - Naumov, Sergej

AU - Mehnert, Reiner

AU - Langguth, Helmut

AU - Sukhov, Fedor F

AU - Orlov, Aleksei Yu

AU - Knolle, W.

AU - Feldman, Vladimir I.

PY - 2002

DA - 2002/02/11 00:00:00

PB - Royal Society of Chemistry (RSC)

SP - 687-699

IS - 3

VL - 2

SN - 0300-9580

SN - 1364-5471

ER -

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@article{2002_Knolle,

author = {Igor Janovský and Sergej Naumov and Reiner Mehnert and Helmut Langguth and Fedor F Sukhov and Aleksei Yu Orlov and W. Knolle and Vladimir I. Feldman},

title = {EPR study of methyl and ethyl acrylate radical cations and their transformations in low-temperature matrices},

journal = {Journal of the Chemical Society Perkin Transactions 2},

year = {2002},

volume = {2},

publisher = {Royal Society of Chemistry (RSC)},

month = {feb},

url = {https://doi.org/10.1039%2Fb105384c},

number = {3},

pages = {687--699},

doi = {10.1039/b105384c}

}

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Knolle, W., et al. “EPR study of methyl and ethyl acrylate radical cations and their transformations in low-temperature matrices.” Journal of the Chemical Society Perkin Transactions 2, vol. 2, no. 3, Feb. 2002, pp. 687-699. https://doi.org/10.1039%2Fb105384c.

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