Cycloalkane and cycloalkene C-H bond dissociation energies

Zhixin Tian, Alireza Fattahi, Lev Lis, Steven R. Kass

Research output: Contribution to journalArticle

51 Scopus citations

Abstract

Both C-H bond dissociation energies for cyclobutene were measured in the gas phase (BDE = 91.2 ± 2.3 (allyl) and 112.5 ± 2.5 (vinyl) kcal mol-1) via a thermodynamic cycle by carrying out proton affinity and electron-binding energy measurements on 1- and 3-cyclobutenyl anions. The results were compared to those for an acyclic model compound, cis-2-butene, and provide the needed information to experimentally establish the heat of formation of cyclobutadiene. Chemically accurate G3 and W1 calculations also were carried out on cycloalkanes, cycloalkenes, and selected reference compounds. It appears that commonly cited bond energies for cyclopropane, cyclobutane, and cyclohexane are 3 to 4 kcal mol-1 too small and their π bond strengths, as given by BDE1 - BDE2, are in error by up to 8 kcal mol -1.

Original languageEnglish (US)
Pages (from-to)17087-17092
Number of pages6
JournalJournal of the American Chemical Society
Volume128
Issue number51
DOIs
StatePublished - Dec 27 2006

Fingerprint Dive into the research topics of 'Cycloalkane and cycloalkene C-H bond dissociation energies'. Together they form a unique fingerprint.

  • Cite this