Thermal stability of the phenylacetylide anion

Casanova, Joseph; Geisel, Manfred; Morris, Randall N.

doi:10.1021/ja01036a077

Cited by 4 publications

(3 citation statements)

References 1 publication

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“…EA(PhCC) ) D(PhCC-H) + IP(H) -∆H acid (6) methods (DFT) predict electron affinities in qualitative agreement with the crude electron affinity estimated with the abovediscussed experimental assumptions (3.26 eV); the electron affinity for the phenylethynyl radical at the B3LYP/DZP++ method is 3.00 eV. Second-order Møller-Plesset perturbation theory (MP2) predicts electron affinities about 1 eV larger than the DFT methods; however, the CCSD(T)/DZP++//MP2/ DZP++ electron affinity of 3.03 eV is in good agreement with those emanating from DFT.…”

Section: Resultsmentioning

confidence: 99%

“…Casanova, Geisel, and Morris (1969) studied the thermal stability of the phenylethynyl anion (PhC⋮C - ). The thermal rearrangement of this anion with respect to phenylethyne-1- 13 C was assumed to be a first-order rearrangement (Δ H ≥37.4 kcal/mol) in polar solvents…”

Section: Introductionmentioning

confidence: 99%

“…a The ZPVE-corrected electron affinities are listed in parentheses. EA(PhCC) ) D(PhCC-H) + IP(H) -∆H acid(6) …”

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confidence: 99%

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π and σ-Phenylethynyl Radicals and Their Isomerso-,m-, andp-Ethynylphenyl: Structures, Energetics, and Electron Affinities

et al. 2008

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Molecular structures, energetics, vibrational frequencies, and electron affinities are predicted for the phenylethynyl radical and its isomers. Electron affinities are computed using density functional theory, -namely, the BHLYP, BLYP, B3LYP, BP86, BPW91, and B3PW91 functionals-, employing the double-zeta plus polarization DZP++ basis set; this level of theory is known to perform well for the computation of electron affinities. Furthermore, ab initio computations employing perturbation theory, coupled cluster with single and double excitations [CCSD], and the inclusion of perturbative triples [CCSD(T)] are performed to determine the relative energies of the isomers. These higher level computations are performed with the correlation consistent family of basis sets cc-pVXZ (X = D, T, Q, 5). Three electronic states are probed for the phenylethynyl radical. In C2v symmetry, the out-of-plane (2B1) radical is predicted to lie about 10 kcal/mol below the in-plane (2B2) radical by DFT methods, which becomes 9.4 kcal/mol with the consideration of the CCSD(T) method. The energy difference between the lowest pi and sigma electronic states of the phenylethynyl radical is also about 10 kcal/mol according to DFT; however, CCSD(T) with the cc-pVQZ basis set shows this energy separation to be just 1.8 kcal/mol. The theoretical electron affinities of the phenylethynyl radical are predicted to be 3.00 eV (B3LYP/DZP++) and 3.03 eV (CCSD(T)/DZP++//MP2/DZP++). The adiabatic electron affinities (EAad) of the three isomers of phenylethynyl, that is, the ortho-, meta-, and para-ethynylphenyl, are predicted to be 1.45, 1.40, and 1.43 eV, respectively. Hence, the phenylethynyl radical binds an electron far more effectively than the three other radicals studied. Thermochemical predictions, such as the bond dissociation energies of the aromatic and ethynyl C-H bonds and the proton affinities of the phenylethynyl and ethynylphenyl anions, are also reported.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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π and σ-Phenylethynyl Radicals and Their Isomerso-,m-, andp-Ethynylphenyl: Structures, Energetics, and Electron Affinities

et al. 2008

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Substituent and H/D randomization in the mass spectra of substituted diphenylacetylenic compounds

Safe¹

1973

Org. Mass Spectrom.

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The mass spectra of several substituted diphenylacetylenes are repxted and the [metastable ion]/[daughter ion] ratios for the isomeric chloro-and bromodiphenylacetylenes suggested substituent scrambling in their respective molecular ions. The metastable ion data also indicated equilibration of the chloro substituents in a series of isomeric dichlorodiphenylacetylenes. In addition, Halogenated diphenylucetylenic compoundsThe isomeric chlorodiphenylacetylenic (I, X = 2-, 3-and 4-chloro) and bromodiphenylacetylenic (I, X = 2-, 3-and 4-bromo) compounds all exhibit a common 2 * Issued as NRCC No. 13254. I329

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Generation of Carbenes and Nitrenes and Their Rearrangements in the Gas Phase

1980

Organic Chemistry

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Thermal stability of the phenylacetylide anion

Cited by 4 publications

References 1 publication

π and σ-Phenylethynyl Radicals and Their Isomerso-,m-, andp-Ethynylphenyl: Structures, Energetics, and Electron Affinities

π and σ-Phenylethynyl Radicals and Their Isomerso-,m-, andp-Ethynylphenyl: Structures, Energetics, and Electron Affinities

Substituent and H/D randomization in the mass spectra of substituted diphenylacetylenic compounds

Generation of Carbenes and Nitrenes and Their Rearrangements in the Gas Phase

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