EVIDENCE FOR STEPWISE NITROGEN EXTRUSION AND RING EXPANSION UPON PHOTOLYSIS OF PHENYL AZIDE
EVIDENCE FOR STEPWISE NITROGEN EXTRUSION AND RING EXPANSION UPON PHOTOLYSIS OF PHENYL AZIDE
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DOI：
10.1021/ja00072a013
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发表时间：
1993-09-22
影响因子：
15
通讯作者：
PLATZ, MS
中科院分区：
文献类型：
--
作者：
MARCINEK, A;LEYVA, E;PLATZ, MS
研究了两种独立的苯基亚硝基前体光解产物的温度依赖性。在二乙胺存在下，叠氮苯基和苯磺酰亚胺光解生成的产物中间体（三联体苯基亚硝基和烯基亚胺）的性质随温度的变化具有相同的定性变化。已知的稳定产物分布的温度依赖性不是由亚硝基前体的激发态引起的。这些数据与单线态苯硝基烯的逐步形成和随后的氮杂环庚四烯的扩张相一致。用能量转移法测定了叠氮苯的单线态和三重态能。
The temperature dependence of the products formed on photolysis of two independent precursors of phenylnitrene has been studied. The identity of the product-forming intermediates (triplet phenylnitrene versus ketene imine) produced on photolysis of phenyl azide and benzenesulfoximine in the presence of diethylamine show the same qualitative variation with temperature. An excited state of the nitrene precursor is not responsible for the known temperature dependence of the distribution of stable products. The data are consistent with stepwise formation of singlet phenylnitrene and subsequent expansion to azacycloheptatetraene. The singlet and triplet energies of phenyl azide have been determined by energy transfer.