Calculations on tunneling in the reactions of noradamantyl carbenes

Sebastian Kozuch, Xue Zhang, David A. Hrovat, Weston Thatcher Borden

Research output: Contribution to journalArticlepeer-review

40 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)17274-17277
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number46
DOIs
StatePublished - 20 Nov 2013
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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