Moss Robert A, Sauers Ronald R, Sheridan Robert S, Tian Jingzhi, Zuev Peter S
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, NJ 08903, USA.
J Am Chem Soc. 2004 Aug 25;126(33):10196-7. doi: 10.1021/ja0488939.
Irradiation of 3-(3-noradamantyl)-3-chlorodiazirine produced the corresponding noradamantylchlorocarbene, which could be detected in solution with laser flash photolysis via its pyridinium ylide, and in N2 or Ar matrixes at 9 K with IR and UV/vis spectroscopy. At ambient temperatures, or on irradiation in the cryogenic matrixes, the carbene rearranged to 2-chloro-1-adamantene, which could be trapped in solution and which was characterized by IR and UV/vis at low temperatures. In the dark at 9 K, the carbene also slowly ring-expanded to the chloroadamantene, at a rate ca. 10111 times faster than predicted by its B3LYP-calculated activation barrier. It is proposed that the low-temperature rearrangement occurs through carbon quantum mechanical tunneling.
对3-(3-降金刚烷基)-3-氯二氮杂环丙烷进行辐照会产生相应的降金刚烷基氯卡宾，该卡宾可通过其吡啶叶立德在溶液中用激光闪光光解检测到，也可在9 K的氮气或氩气基质中用红外光谱和紫外/可见光谱检测到。在环境温度下，或在低温基质中进行辐照时，卡宾会重排为2-氯-1-金刚烯，该产物可在溶液中捕获，并在低温下通过红外光谱和紫外/可见光谱进行表征。在9 K的黑暗环境中，卡宾也会缓慢地环扩展为氯代金刚烯，其速率比通过B3LYP计算的活化能垒预测的速率快约10^-11倍。有人提出，低温重排是通过碳量子力学隧穿发生的。
