Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ-Bonded Species by Time-Resolved UV/Vis and IR Spectroscopy.
Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ-Bonded Species by Time-Resolved UV/Vis and IR Spectroscopy.
复制标题
通过时间分辨紫外/可见光和红外光谱直接检测局域单线态双自由基与其 σ 键合物种之间的化学平衡。
作者：
Shohei Yoshidomi;Megumi Mishima;S. Seyama;M. Abe;Y. Fujiwara;T. Ishibashi
定域单重态双自由基是键均解的关键中间体。单重态双自由基在能量上远不如σ键物种稳定。通常，仅观察到从双自由基到σ键合物种的单向反应。在这项研究中，一个单线态的1，2-二氮杂环戊烷-3，5-二基自由基和相应的σ-键物种之间的热平衡被直接观察到。单重态自由基比σ键自由基更稳定。溶剂效应澄清了关键特征，如单重态双自由基的两性离子特征。详细讨论了氮原子的影响。
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.
影响因子：
21.8
作者：
Rudebusch, Gabriel E.;Zafra, Jose L.;Haley, Michael M.
通讯作者：
Haley, Michael M.
影响因子：
16.6
作者：
Beweries, Torsten;Kuzora, Rene;Villinger, Alexander
通讯作者：
Villinger, Alexander