Zhang Yunlong, Kubicki Jacek, Platz Matthew S
Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA.
J Am Chem Soc. 2009 Sep 30;131(38):13602-3. doi: 10.1021/ja905992p.
Ultrafast UV-vis/IR spectroscopies were used to study the photochemistry of a vinyl diazo ester PhCH=CHCN2CO2CH3 (1) in solution. The results indicate that singlet styrylcarbomethoxy carbene ((1)2) is produced from the excited state of diazo precursor (1*). It is concluded that vinyl singlet carbene ((1)2) undergoes an intramolecular cyclopropenation reaction to produce the cyclopropene product (3), and undergoes intersystem crossing to ground triplet carbene ((3)2). The predictions of DFT calculations are consistent with the observations.
利用超快紫外-可见/红外光谱研究了乙烯基重氮酯PhCH=CHCN2CO2CH3（1）在溶液中的光化学性质。结果表明，单线态苯乙烯基甲氧基卡宾（(1)2）由重氮前体（1*）的激发态产生。得出的结论是，乙烯基单线态卡宾（(1)2）发生分子内环丙烷化反应生成环丙烯产物（3），并发生系间窜越生成基态三线态卡宾（(3)2）。密度泛函理论计算的预测结果与观测结果一致。
