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Tyurin, Daniil A.; Belevskii, V. N.

doi:10.1023/a:1012534725443

Cited by 7 publications

(10 citation statements)

References 9 publications

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“…Furthermore, the irradiated samples exhibit an orange-reddish color, which disappears under exposure to visible light, simultaneously with transformation of the ESR signal (see below). This observation is in line with data on the optical absorption spectra of ether radical cations, which show strong absorption bands in the visible region (maximums at 430-440 nm) [12,13]. Note that none of the possible products of secondary transformations of MPE radical cations (distonic radical cations and neutral radicals) exhibits absorption in the visible spectral region [19].…”

Section: Resultssupporting

confidence: 86%

“…Thus, reaction (1) occurs both at an increased concentration of the ether in the matrices of Freon-11 and Freon-113 (directly at 77 K) and under the conditions when molecular mobility is frozen out near the phase transition point (at 110-115 K) in a Freon-113 matrix. Similar behavior was found for most ether radical cations studied previously [5,9,13].…”

Section: Thermal Reactionssupporting

confidence: 87%

“…This radical dominates in the ESR spectra of 4% MPE in CFCl 3 . An isotropic triplet with the splitting of a(2ç) = 1.75 mT is observed in the ESR spectra recorded at 140 K. Such a triplet should be assigned to the n-PrO radical resulting from ionmolecule reaction (1) (proton transfer from the maximum spin density position), which occurs during irradiation at high ether concentrations and is typical of radical cations of a number of ethers [5,9,10,13]. In the case of irradiation of deuterated MPE (2% in CFCl 3 ), the ESR spectrum recorded at 77 K exhibits a singlet signal.…”

Section: Thermal Reactionsmentioning

confidence: 94%

“…On the other hand, it was found that the radical cations of methyl tert -butyl ether (MTBE) were stable at 77 K in polycrystalline freonic matrices [13]. These radical cations undergo rearrangements involving the tert -butyl group upon heating or under the action of light [13].…”

mentioning

confidence: 99%

“…These radical cations undergo rearrangements involving the tert -butyl group upon heating or under the action of light [13]. Thus, the nature of alkyl substituents may have a substantial effect on the structure and reactivity of the radical cations of ethers.…”

mentioning

confidence: 99%

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Experimental and theoretical study on the structure and reactions of 1-methoxypropane radical cations

2005

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Structure and mechanism of thermal and photochemical reactions of radical cations of methyl npropyl ether (MPE) were studied in irradiated freonic matrices CFCl 3 , CF 2 ClCFCl 2 , and CF 3 ë Cl 3 at 77 K. The quantum chemical calculations of the structure of radical cations and products of their transformations were carried out with methods based on the density functional theory (DFT). Experimental and calculation results show that the MPE radical cations are characterized by substantial delocalization of spin density to the propyl group. The action of light on the MPE radical cations in a CF 3 CCl 3 matrix at 77 K results in intramolecular rearrangement yielding the distonic radical cation ëç 2 ëç 2 ( O ç + ) CH 3 . It was found that the primary MPE radical cations underwent irreversible transformation to ëç 3 ëç 2 ëç 2 radical as a result of an ionmolecule reaction that occurred in a CF 2 ClCFCl 2 matrix upon heating the sample to 110-120 K or in a CFCl 3 matrix upon increasing the solute concentration. CH . 2 OCH 2 .

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Section: Resultssupporting

confidence: 86%

Section: Thermal Reactionssupporting

confidence: 87%