title: Experimental and computational bridgehead C-H bond dissociation enthalpies.
abstract: Bridgehead C-H bond dissociation enthalpies of 105.7 ± 2.0, 102.9 ± 1.7, and 102.4 ± 1.9 kcal mol(-1) for bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, and adamantane, respectively, were determined in the gas phase by making use of a thermodynamic cycle (i.e., BDE(R-H) = ΔH°(acid)(H-X) - IE(H(·)) + EA(X(·))). These results are in good accord with high-level G3 theory calculations, and the experimental values along with G3 predictions for bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[3.1.1]heptane, and bicyclo[4.2.1]nonane were found to correlate with the flexibility of the ring system. Rare examples of alkyl anions in the gas phase are also provided.
authors.affiliation: Department of Chemistry, Sharif University of Technology, Tehran, Iran. fattahi@sharif.edu
authors.forename: Alireza
authors.initials: A
authors.lastname: Fattahi
authors.forename: Lev
authors.initials: L
authors.lastname: Lis
authors.forename: Zahra A
authors.initials: ZA
authors.lastname: Tehrani
authors.forename: Sudha S
authors.initials: SS
authors.lastname: Marimanikkuppam
authors.forename: Steven R
authors.initials: SR
authors.lastname: Kass