Solution phase isomerization of vibrationally excited singlet nitrenes to vibrationally excited 1,2-didehydroazepine
Solution phase isomerization of vibrationally excited singlet nitrenes to vibrationally excited 1,2-didehydroazepine
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DOI：
10.1021/ja065783o
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发表时间：
2006-11-22
影响因子：
15
通讯作者：
Platz, Matthew S.
中科院分区：
文献类型：
--
作者：
Burdzinski, Gotard T.;Middleton, Chris T.;Platz, Matthew S.
苯基和双苯基叠氮化物的光解（270 nm）释放出振动激发的单线态亚硝基，该亚硝基以与热弛豫相竞争的速率异构成相应的热1,2-二脱氢氮卓。利用超快振动光谱技术，我们观察到在环境温度下，叠氮苯基在氯仿中光解和叠氮对联苯在乙腈中光解后，在皮秒内形成了振动激发的1,2,4,6 -氮杂环庚四烯（1,2-二脱氢氮平）。
Photolysis of phenyl ando-biphenylyl azide (at 270 nm) releases vibrationally excited singlet nitrene which isomerizes to the corresponding hot 1,2-didehydroazepine at a rate competitive with thermal relaxation. Using ultrafast vibrational spectroscopy we observe the formation of vibrationally excited 1,2-4,6-azacycloheptatetraene (1,2-didehydroazepine) in picoseconds following photolysis of phenyl azide in chloroform ando-biphenylyl azide in acetonitrile at ambient temperature.