Electrophilic Aromatic Nitrosation. Isolation and X-ray Crystallography of the Metastable NO+ Complex With Nitrosoarene

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Royal Society of Chemistry

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Journal of the Chemical Society, Perkin Transactions 2

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Isolation of the unstable 1∶1 complex of 4-nitrosoanisole with NO+PF6 allows its precise X-ray structural characterization. The charge-transfer crystal is formed via strong N⋯N coordination [the distance of 1.938(5) Å corresponding to a σ-bond order of ≈0.2] in the mean plane of the planar 4-nitrosoanisole donor. Thorough analysis of its molecular geometry in terms of valence resonance and MO schemes reveals a strong charge polarization with a local negative charge localized on the nitroso group and a local positive charge distributed over the adjacent p-methoxybenzyl moiety. Such a charge distribution accommodates the well-known passivation of nitrosoarenes to multiple nitrosation and explains the ease of demethylation of the complex. Comparison of a variety of nitroso- and nitroarene structures has shown that the nitrosoarene experiences a much stronger quinoidal distortion of the aromatic ring as compared with the latter. This indicates a stronger electron-withdrawing effect of the nitroso group relative to that of the nitro group. The weakened aromatic resonance in the nitrosoarenes could be responsible for the observed slower rate and the measurable isotope effect in electrophilic nitrosation as opposed to nitration.


Journal of the Chemical Society, Perkin Transactions 2, No. 9 (2000): 1919-1923. DOI.