Nongeneral Character of the Resonance Parameters Σ R + of Silicon-, Germanium-, and Tin-Containing Substituents in Radical Cations
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The resonance parameters σ R + of substituents Y in radical cations YD+· [where D is a π- or n-type center, and Y = MMe3, CH2MMe3 (M = Si, Ge, Sn), C(SiMe3)3] depend on the nature of both Y and D. Using radical cations YD+· (Y = CH2SiMe3, SnMe3) as examples, it was found that the two conjugation parameters, constants σ R + of substituents Y and perturbation energy calculated by the modified molecular orbital perturbation method, are linearly related to each other. The energies of donor and acceptor components of the overall resonance effect of CH2SiMe3 and SnMe3 with respect to radical cation centers D+· were estimated for the first time. The donor energy constituent in YD+· is considerably greater than in neutral DY molecules.
KeywordsSilicon Organic Chemistry Germanium Radical Cation Perturbation Method
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