Journal of the Chemical Society. Perkin transactions II p. 941 - 948 (1980)
Update date:2022-08-17
Topics:
Barker, Philip J.
Davies, Alwyn G.
Tse, Man-Wing
Cyclopentadienyl derivatives of tin(IV) and mercury(II) and alkylcyclopentadienyl derivatives of mercury(II) are photolysed in solution to show the e.s.r. spectra of the appropriate radicals RC5H4. (R = H, D, Me, Et, Pri, or But).The C5H5. radical is a planar ?-radical with average D5h symmetry, and its spectrum is broadened in the presence of organic bromides, perhaps by a charge-transfer mechanism.The introduction of alkyl groups breaks the degeneracy of the ψA and ψS molecular orbitals of the ?-system by electron release, destabilising the ψS MO, and the e.s.r. spectrum reflects the spin density distribution in the configuration ψA2ψS1.Deuterium has a small but detectable perturbing effect: the ψA MO is destabilised by ca. 100 J mol-1, and thermal mixing of the two energy levels results in the configuration ψS1.515ψA1.485.This is compatible with the model of a vibrational perturbation of the resonance integral β, rather than of the Coulomb integral α.
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