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An electron spin resonance study of the effect of group IV substituents in cyclopentadienyl radicals

Journal Article


Abstract


  • E.s.r. spectra have been recorded in solution for the substituted cyclopentadienyl radicals X3MC5H4., where X3M = Me3Si, Me2HSi, Me2ClSi, Me2FSi, Ph2ClSi, Cl3Si, Me3Ge, Bu3Ge, Ph2ClGe, and Me3Sn. The spectra can be interpreted in terms of perturbation of the orbitals ψA and ψS which are degenerate in the C5H5. radical. This allows the substituents to be placed in the following sequence regarding their electronic interactions, compared with that of hydrogen, with the ψS MO of the cyclopentadienyl π-system: electron repelling, Me3C ≫ Bu3Ge ∼ Me3Ge > H; electron attracting, H < Me3Sn < Me3Si < Me2HSi < Me2ClSi < Ph2ClGe < Me 2FSi < Ph2ClSi < Cl3Si.

Publication Date


  • 1982

Citation


  • Barker, P. J., Davies, A. G., Henriquez, R., & Nedelec, J. Y. (1982). An electron spin resonance study of the effect of group IV substituents in cyclopentadienyl radicals. Journal of the Chemical Society, Perkin Transactions 2, (6), 745-750. doi:10.1039/p29820000745

Scopus Eid


  • 2-s2.0-37049093685

Start Page


  • 745

End Page


  • 750

Issue


  • 6

Abstract


  • E.s.r. spectra have been recorded in solution for the substituted cyclopentadienyl radicals X3MC5H4., where X3M = Me3Si, Me2HSi, Me2ClSi, Me2FSi, Ph2ClSi, Cl3Si, Me3Ge, Bu3Ge, Ph2ClGe, and Me3Sn. The spectra can be interpreted in terms of perturbation of the orbitals ψA and ψS which are degenerate in the C5H5. radical. This allows the substituents to be placed in the following sequence regarding their electronic interactions, compared with that of hydrogen, with the ψS MO of the cyclopentadienyl π-system: electron repelling, Me3C ≫ Bu3Ge ∼ Me3Ge > H; electron attracting, H < Me3Sn < Me3Si < Me2HSi < Me2ClSi < Ph2ClGe < Me 2FSi < Ph2ClSi < Cl3Si.

Publication Date


  • 1982

Citation


  • Barker, P. J., Davies, A. G., Henriquez, R., & Nedelec, J. Y. (1982). An electron spin resonance study of the effect of group IV substituents in cyclopentadienyl radicals. Journal of the Chemical Society, Perkin Transactions 2, (6), 745-750. doi:10.1039/p29820000745

Scopus Eid


  • 2-s2.0-37049093685

Start Page


  • 745

End Page


  • 750

Issue


  • 6