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Structure and Structural Nonrigidity of Tetrachlorodibenzo-p-Dioxin Radical Cations

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Abstract

Ab initio calculations showed that the tetrachlorodibenzo-para-dioxin radical cations (TCDD RCs) with a planar structure have two steady states with asymmetric dioxin cycles. The activation barriers between these states are up to 2 kcal/mole, so that the RCs may be regarded as being structurally nonrigid within the dioxin cycle. The 2,3,7,8-TCDD RC is more stable than the 1,4,6,9-TCDD RC, the energy difference being 5.2 kcal/mole. The adiabatic ionization potential of 2,3,7,8-TCDD (7.54 eV) is 0.1 eV smaller than the corresponding potential of 1,4,6,9-TCDD. These factors account for the increased hemoproteide affinity and hence increased biological activity of 2,3,7,8-TCDD.

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  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow

    Yu. A. Borisov

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  1. Yu. A. Borisov
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  2. A. F. Kolomiets
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Borisov, Y.A., Kolomiets, A.F. Structure and Structural Nonrigidity of Tetrachlorodibenzo-p-Dioxin Radical Cations. Journal of Structural Chemistry 44, 877–879 (2003). https://doi.org/10.1023/B:JORY.0000029829.21349.83

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