Calculations on Tunneling in the Reactions of Noradamantyl Carbenes

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• 作者：Sebastian Kozuch ; Xue Zhang ; David A. Hrovat ; Weston Thatcher Borden
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：November 20, 2013
• 年：2013
• 卷：135
• 期：46
• 页码：17274-17277
• 全文大小：235K
• 年卷期：v.135,no.46(November 20, 2013)
• ISSN：1520-5126

文摘

Noradamantylchlorocarbene has been found experimentally to undergo ring expansion to 2-chloroadamantene at cryogenic temperatures. The rate constant, calculated with inclusion of small-curvature tunneling, is within a factor of 2 of the rate constant measured at 9 K in a nitrogen matrix. Our calculations predict that noradamantylfluorocarbene will not be found to rearrange under these conditions. The rate constant for carbon tunneling in the ring expansion of noradamantylmethylcarbene (1d) to 2-methyladamantene at T 10 K is calculated to be lower by more than 8 orders of magnitude than the rate constant for formation of 3-vinylnoradamantane from 1d by hydrogen migration.