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Electron inity of 1,3,5,7-cyclooctatetraene determined by the kinetic method

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Journal of the American Society for Mass Spectrometry

Abstract

The kinetic method is used to determine the electron inity (EA) of 1,3,5,7-cyclooctatetraene (COT), a compound that undergoes a significant structural change upon electron attachment. Collision-induced dissociation of anionic clusters of COT with a set of reference compounds (Ref), [COT·Ref]−·, at various collision energies, allowed deconvolution of the relative enthalpies and entropies of the competitive reactions. The adiabatic EA of COT is determined to be 0.58±0.10 eV, in good agreement with the value, 0.58±0.04 eV, of Wentworth and Ristau (J. Phys. Chem. 1969, 73, 2126) determined by thermal electron detachment as well as the more recent value, 0.55±0.02 eV, of Kato et al. (J. Am. Chem. Soc. 1997, 119, 7863) determined by equilibrium electron transfer with molecular oxygen. A large entropy difference, 25.6±10.0 e.u. (J mol−1 K−1), is observed between the two dissociation channels. This entropy difference corresponds to a negative 14.7±13.0 e.u. change for the dissociation of the dimer to give COT−· and the neutral reference compound and a positive 10.9±8.4 e.u. entropy change for the dissociation of the dimer to give Ref−· and neutral COT.

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Authors and Affiliations

  1. Department of Chemistry, Purdue University, West Lafayette, Indiana, USA

    Jeff W. Denault, Guodong Chen & R. Graham Cooks

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  1. Jeff W. Denault
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  2. Guodong Chen
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  3. R. Graham Cooks
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Correspondence to R. Graham Cooks.

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Denault, J.W., Chen, G. & Cooks, R.G. Electron inity of 1,3,5,7-cyclooctatetraene determined by the kinetic method. J Am Soc Mass Spectrom 9, 1141–1145 (1998). https://doi.org/10.1016/S1044-0305(98)00092-0

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  • DOI: https://doi.org/10.1016/S1044-0305(98)00092-0

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