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Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ‐Bonded Species by Time‐Resolved UV/Vis and IR Spectroscopy
Abstract:Localized singlet diradicals are key intermediates in bond homolyses. The singlet diradicals are energetically much less stable than the σ‐bonded species. In general, only one‐way reactions from diradicals to σ‐bonded species are observed. In this study, a thermal equilibrium between a singlet 1,2‐diazacyclopentane‐3,5‐diyl diradical and the corresponding σ‐bonded species was directly observed. The singlet diradical was more stable than the σ‐bonded species. The solvent effect clarified key features, such as the zwitterionic character of the singlet diradical. The effect of the nitrogen atoms is discussed in detail.
Keywords:Azoverbindungen  Photochemie  Radikale  Reaktionsmechanismen  Reaktive Zwischenstufen
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