Is the tropylium ion (Tr+) formed from toluene at its thermochemical threshold?

Lifshitz, Chava; Gotkis, Yehiel; Ioffe, A.; Laskin, Julia; Shaik, Sason

doi:10.1016/0168-1176(93)80020-f

Cited by 67 publications

(126 citation statements)

References 18 publications

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“…TS2 was not found in the literature. The Article by Lifshitz states that there is some uncertainty about the exact energy of TS2, but it is definitely considerably lower than the energy of TS1 [19]. The energy presented here is contrary to this statement in that the TS2 energy is slightly higher than the energy of TS1 with density functional theory.…”

Section: Resultscontrasting

confidence: 73%

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Theoretical investigation of the formation of the tropylium ion from the toluene radical cation

Bullins

Huang

Kirkby

2009

Int J of Quantum Chemistry

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ABSTRACT:The formation of the tropylium ion, C 7 H 7 ϩ , in the mass spectrum of toluene is a chemical process that has been extensively studied. There is, however, still debate as to the structure of the moieties and the reaction pathways involved. This work presents the first computationally complete reaction schemes for the formation of tropylium from toluene to be reported. The calculations were performed at the HF/6-31G(d, p) and the DFT/B3LYP/6-311ϩϩG(2d) levels of theory using Gaussian 03W. The previously unreported optimized structures and energies for a transition state and an intermediate in one scheme and a transition state in the other have been determined. These results are consistent with the previously reported literature and the available experimental data.

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Section: Resultscontrasting

confidence: 73%

“…These new results are a completion of the mechanism at this level of theory. The energies calculated with DFT/B3LYP/6-311ϩϩG(2d) are comparable with the values calculated with G2(MP2, SVP) by Moon et al [8] and those of Lifshitz et al [19]. The latter are the arithmetic mean of values calculated by PMP3, MP4SDTQ, and QCISD(T)//HF/3-21G.…”

Section: Resultsmentioning

confidence: 65%

Theoretical investigation of the formation of the tropylium ion from the toluene radical cation

Bullins

Huang

Kirkby

2009

Int J of Quantum Chemistry

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“…These ions are formed by direct ionization of a molecule of known structure or elemental formula, and are used to verify by comparison the structure or thermochemistry of an unknown ion or to calibrate the m/z scale of the mass spectrometer. From [287][288][289].…”

Section: Reference Ionmentioning

confidence: 99%

Definitions of terms relating to mass spectrometry (IUPAC Recommendations 2013)

Murray

Boyd

Eberlin

et al. 2013

Pure and Applied Chemistry

342

224

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This document contains recommendations for terminology in mass spectrometry. Development of standard terms dates back to 1974 when the IUPAC Commission on Analytical Nomenclature issued recommendations on mass spectrometry terms and definitions. In 1978, the IUPAC Commission on Molecular Structure and Spectroscopy updated and extended the recommendations and made further recommendations regarding symbols, acronyms, and abbreviations. The IUPAC Physical Chemistry Division Commission on Molecular Structure and Spectroscopy's Subcommittee on Mass Spectroscopy revised the recommended terms in 1991 and appended terms relating to vacuum technology. Some additional terms related to tandem mass spectrometry were added in 1993 and accelerator mass spectrometry in 1994. Owing to the rapid expansion of the field in the intervening years, particularly in mass spectrometry of biomolecules, a further revision of the recommendations has become necessary. This document contains a comprehensive revision of mass spectrometry terminology that represents the current consensus of the mass spectrometry community.

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“…Recently, the isomerization and dissociation mechanisms of some ionized monosubstituted benzenes, C6H5XHn +• (X = C, N, O, Si, P, S, and As), have been proposed using quantum chemical calculations. [2][3][4][5][6][7][8][9][10] Both similarities and differences were found among their dissociation mechanisms. Ring expansion to seven-membered ring isomers is a common mechanism for theses molecular ions.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11][12][13] Their reaction kinetics has often been understood by exploring the potential energy surfaces for the isomerizations and the dissociations. Ionized benzene derivatives are among the most interesting subjects to gas phase ion chemists.…”

Section: Introductionmentioning

confidence: 99%

Dissociation of the Phenylarsane Molecular Ion: A Theoretical Study

Kim¹,

Choe

2010

Bulletin of the Korean Chemical Society

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The potential energy surfaces (PESs) for the primary and secondary dissociations of the phenylarsane molecular ion (1a) were determined from the quantum chemical calculations using the G3(MP2)//B3LYP method. Several pathways for the loss of H• were determined and occurred though rearrangements as well as through direct bond cleavages. The kinetic analysis based on the PES for the primary dissociation showed that the loss of H2 was more favored than the loss of H•, but the H• loss competed with the H2 loss at high energies. The bicyclic isomer, 7-arsa-norcaradiene radical cation, was formed through the 1,2 shift of an α-H of 1a and played an important role as an intermediate for the further rearrangements in the loss of H• and the losses of As• and AsH. The reaction pathways for the formation of the major products in the secondary dissociations of [M-H] + and [M-H2] +• were examined. The theoretical prediction explained the previous experimental results for the dissociation at high energies but not the dissociation at low energies.

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Is the tropylium ion (Tr+) formed from toluene at its thermochemical threshold?

Cited by 67 publications

References 18 publications

Theoretical investigation of the formation of the tropylium ion from the toluene radical cation

Theoretical investigation of the formation of the tropylium ion from the toluene radical cation

Definitions of terms relating to mass spectrometry (IUPAC Recommendations 2013)

Dissociation of the Phenylarsane Molecular Ion: A Theoretical Study

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