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Ionization potentials of halides. Substituent effects in Cl-, Br-, and I-centered radical cations

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Abstract

The first vertical ionization potentials (I) of halides HalX (Hal = Cl, Br, I; X is an inorganic or organic substituent) are linearly related to the inductive (σI), resonance (σR +), and polarizability (σα) constants of the substituents X (I = a + bσI + cσR + + dσα). As the atomic number of the Hal element in the Hal·+X radical cations increases, the inductive interaction is strengthened while the polarizability interaction is weakened. Conjugation remains virtually independent of the Hal atom. The resonance σR +-constants of the MX3 (M = Si, Ge, Sn, Pb) substituents bound to the Hal·+ radical cation centers were first calculated.

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Authors and Affiliations

  1. G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603950, Nizhnii Novgorod, Russian Federation

    A. N. Egorochkin & O. V. Kuznetsova

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  1. A. N. Egorochkin
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  2. O. V. Kuznetsova
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Egorochkin, A.N., Kuznetsova, O.V. Ionization potentials of halides. Substituent effects in Cl-, Br-, and I-centered radical cations. Russian Chemical Bulletin 52, 312–319 (2003). https://doi.org/10.1023/A:1023438211658

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