Effects of Fluorine on the Structures and Energetics of the Propynyl and Propargyl Radicals and Their Anions

Sreeruttun, Raj K.; Ramasami, Ponnadurai; Wannere, Chaitanya S.; Paul, Ankan; Schleyer, Paul von Ragué; Schaefer, Henry F.

doi:10.1021/jo0507688

Cited by 10 publications

(26 citation statements)

References 37 publications

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“…21͒ eV. The presence of such a low-lying degenerate excited state can cause artificial symmetry breaking of the wave function in single reference calculations and lead to distortion from the C 3v geometry, 20,26 as has been seen in calculations on the NO 3 radical. 27 Moreover, possible combinations of Jahn-Teller and pseudo-Jahn-Teller effects can lead to a very complicated vibronic spectrum.…”

Section: Introductionmentioning

confidence: 94%

“…This doublet was attributed to a split of the degeneracy of the 2 E ground state in which the unpaired electron is in the orbital of the triple bond, based on the early theoretical work by Bauschlicher and Langhoff. 25 However, subsequent calculations 1,[18][19][20][21][22]26 converged to a 2 A 1 or 2 AЈ ground state with the unpaired electron in a nonbonding sp orbital on the terminal carbon. The "" state has been calculated to be an extremely low-lying excited state with vertical excitation energy between 0.04 ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

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Slow electron velocity-map imaging spectroscopy of the 1-propynyl radical

Zhou

Garand

Eisfeld

et al. 2007

The Journal of Chemical Physics

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High resolution photoelectron spectra of the 1-propynyl and 1-propynyl-d(3) anions acquired with slow electron velocity-map imaging are presented. The electron affinity is determined to be 2.7355+/-0.0010 eV for the 1-propynyl radical and 2.7300+/-0.0010 eV for 1-propynyl-d(3). Several vibronic transitions are observed and assigned using the isotopic shifts and results from ab initio calculations. Good agreement between experimental spectra and calculations suggests a C(3v) geometry for the 1-propynyl radical. No evidence is found for strong vibronic coupling between the ground electronic state and the low-lying first excited state.

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Section: Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Slow electron velocity-map imaging spectroscopy of the 1-propynyl radical

Zhou

Garand

Eisfeld

et al. 2007

The Journal of Chemical Physics

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“…This work reports the gas‐phase basicity of propynyl anions as the difference in the sum of electronic and thermal free energies of the anion and the neutral molecules, as well as the thermal correction to the Gibbs free energy 16…”

Section: Computational Detailsmentioning

confidence: 99%

“…Zhang15 has reported the results of a study of the acidity of the acetylenic proton and the CH bond dissociation enthalpies in fluorine derivatives of propyne and also in the neutrals and radicals of various substrates by ab initio calculations. Sreeruttun et al have observed the effects of fluorine on the structures and energetics of propynyl radicals and their anions 16…”

Section: Introductionmentioning

confidence: 99%

Substituent effect on electron affinity, gas‐phase basicity, and structure of monosubstituted propynyl radicals and their anions: A theoretical study

Lee

2009

J Comput Chem

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The substituent effect of electron-withdrawing groups on electron affinity and gas-phase basicity has been investigated for substituted propynl radicals and their corresponding anions. It is shown that when a hydrogen of the alpha-CH(3) group in the propynyl system is substituted by an electron-withdrawing substituent, electron affinity increases, whereas gas-phase basicity decreases. These results can be explained in terms of the natural atomic charge of the terminal acetylene carbon of the systems. The calculated electron affinities are 3.28 eV (*C=C-CH(2)F), 3.59 eV (*C[triple bond]C-CH(2)Cl) and 3.73 eV (*C[triple bond]C-CH(2)Br), and the gas-phase basicities of their anions are 359.5 kcal/mol ((-):C[triple bond]C-CH(2)F), 354.8 kcal/mol (:C[triple bond]C-CH(2)Cl) and 351.3 kcal/mol ((-):C[triple bond]C-CH(2)Br). It is concluded that the larger the magnitude of electron-withdrawing, the greater is the electron affinity of radical and the smaller is the gas-phase basicity of its anion.

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“…The methylethynyl (also called propynyl) radical (•CCCH 3 ) is a significant chemical in hydrocarbon chemistry 8. Sreeruttun et al 9. have studied the effects of fluorine on the structures and energetics of the derivatives of propynyl (•CCCH 3 ) and propargyl (CHCCH 2 •) radicals and their anions ( − :CCCH 3 and CHCCH 2 : − ).…”

Section: Introductionmentioning

confidence: 99%

Substituent effect on electron affinity, gas‐phase basicity, and structure of monosubstituted propargyl radicals and their anions: a theoretical study

Lee

2009

J of Physical Organic Chem

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The substituent effect of electron‐withdrawing groups on electron affinity and gas‐phase basicity has been investigated for substituted propargyl radicals and their corresponding anions. It is shown that when a hydrogen of the α‐CH2 group or acetylenic CH in the propargyl system is substituted by an electron‐withdrawing substituent, electron affinity increases, whereas gas‐phase basicity decreases. The calculated electron affinities are 0.95 eV (CHCCH2•), 1.15 eV (CHCCHF•), 1.38 eV (CHCCHCl•), 1.48 eV (CHCCHBr•) for the isomers with terminal CH and 1.66 eV (CFCCH2•), 1.70 eV (CClCCH2•), 1.86 eV (CBrCCH2•) for the isomers with terminal CX at B3LYP level. The calculated gas‐phase basicities for their anions are 378.4 kcal/mol (CHCCH2:−), 371.6 kcal/mol (CHCCHF:−), 365.1 kcal/mol (CHCCHCl:−), 363.5 kcal/mol (CHCCHBr:−) for the isomers with terminal CH and 362.6 kcal/mol (CFCCH2:−), 360.4 kcal/mol (CClCCH2:−), 356.3 kcal/mol (CBrCCH2:−) for the isomers with terminal CX at B3LYP level. It is concluded that the larger the magnitude of electron‐withdrawing, the greater is the electron affinity of radical and the smaller is the gas‐phase basicity of its anion. This tendency of the electron affinities and gas‐phase bacisities is greater in isomers with the terminal CX than isomers with the terminal CH. Copyright © 2009 John Wiley & Sons, Ltd.

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Effects of Fluorine on the Structures and Energetics of the Propynyl and Propargyl Radicals and Their Anions

Cited by 10 publications

References 37 publications

Slow electron velocity-map imaging spectroscopy of the 1-propynyl radical

Slow electron velocity-map imaging spectroscopy of the 1-propynyl radical

Substituent effect on electron affinity, gas‐phase basicity, and structure of monosubstituted propynyl radicals and their anions: A theoretical study

Substituent effect on electron affinity, gas‐phase basicity, and structure of monosubstituted propargyl radicals and their anions: a theoretical study

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