3,4,5,6-Tetrafluorophenylnitren-2-yl: A Ground-State Quartet Triradical
3,4,5,6-Tetrafluorophenylnitren-2-yl: A Ground-State Quartet Triradical
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DOI：
10.1002/chem.200903285
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Sander, Wolfram
中科院分区：
文献类型：
--
作者：
Grote, Dirk;Finke, Christopher;Sander, Wolfram
研究了2-碘-3，4，5，6-四氟苯基叠氮化合物（7 d）在氩气和氖中的光化学反应，并用红外光谱和电子顺磁共振谱对产物进行了表征。主要的光化学步骤是氮分子的损失和苯基氮烯1d的形成。进一步用UV或可见光照射，得到1d与氮杂环丙烷5d ′、烯酮亚胺6d ′、氮杂环丙烷自由基2d和氮杂环丙烷自由基9的混合物。这些产物的相对量强烈地取决于基质和照射条件。氮并自由基2d的四重基态，其特征在于通过EPR光谱。结合实验结果的电子结构计算允许详细了解这种不寻常的新型有机高自旋分子的性质。
The photochemistry of 2-iodo-3,4,5,6-tetrafluorophenyl azide (7d) has been investigated in argon and neon matrices at 4 K, and the products characterized by IR and EPR spectroscopy. The primary photochemical step is loss of a nitrogen molecule and formation of phenyl nitrene 1d. Further irradiation with UV or visible light results in mixtures of 1d with azirine 5d', ketenimine 6d', nitreno radical 2d, and azirinyl radical 9. The relative amounts of these products strongly depend on the matrix and on the irradiation conditions. Nitreno radical 2d with a quartet ground state was characterized by EPR spectroscopy. Electronic structure calculations in combination with the experimental results allow for a detailed understanding of the properties of this unusual new type of organic high-spin molecules.