Ionization potentials of non-metal monosulfides. Conjugation in radical cations containing Group IV elements |
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| Authors: | A N Egorochkin M G Voronkov S E Skobeleva T G Mushtina O V Zderenova |
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| Institution: | (1) G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603600 Nizhnii Novgorod, Russian Federation;(2) Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 ul. Favorskogo, 664033 Irkutsk, Russian Federation |
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| Abstract: | The first vertical ionization potentialsI(ns) of 69 monosulfides XSY (X, Y=H, Hal, organic, or heteroorganic substituent) are related to the inductive σI resonance (σ
R
+
) and polarizability (σα) constants of the substituents by dependences of theI(nS)=a+bΣσI+bΣσR+bΣσα type. TheI(ns) values are also affected by hyperconjugation which increases on going from XSH to XSY (Y≠H) compounds. The first calculations
of the σ
R
+
parameters characterizing the conjugation of Si-, Ge-, Sn-, and Pb-containing substituents with the S.+ radical cation center are reported. The reasons for weakening of resonance donor properties of heteroorganic substituents
of the +M-type in the systems studied as compared to those of the same substituents in the corresponding aromatic radical cations are
considered.
Translated fromIzvestiya Akademii Nauk. Seriya Khmicheskaya, No. 1, pp. 25–31, January, 2000. |
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| Keywords: | non-metal monosulfides hydrogen sulfide diorganylsulfides organometallic sulfides derivatives of Group IV elements ionization potentials radical cations conjugation |
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