177552-58-8Relevant articles and documents
Reactivity and thermochemistry of quadricyclane in the gas phase
Lee, Hack Sung,DePuy, Charles H.,Bierbaum, Veronica M.
, p. 5068 - 5073 (2007/10/03)
The gas-phase acidity of quadricyclane C7H8 has been determined using a flowing after-glow selected ion flow tube at room temperature. Measurements of forward and reserve rate constants for the proton transfer reaction B- + C7H8 ? C7H7- + BH where BH = NH3, CH3NH2 and C6H6 give ΔacidG300(C7H8) = 394.7±0.8 kcal/mol and ΔacidH300(C7H8) = 403.0±1.1 kcal/mol. Combining this value with the electron affinity, 0.868±0.006 eV, of the quadricyclyl radical, gives 109.4±1.3 kcal/mol for the C-H bond dissociation energy of quadricyclane at Cl. Reactions of quadricyclane ion with various reagents have been studied, and branching ratios of product channels have been determined. These results along with ab initio calculations and a companion photoelectron spectroscopy study, indicate that there are two isomers of quadricyclane ion which have similar energies. The gas-phase acidity of quadricyclane, C7H8, has been determined using a flowing afterglow-selected ion flow tube at room temperature. Measurements of forward and reverse rate constants for the proton transfer reactions B- + C7H8 ? C7H7- + BH where BH = NH3, CH3NH2, and C6H6 give Δ(acid)G300(C7H8) = 394.7 ± 0.8 kcal/mol and Δ(acid)H300(C7H8) = 403.0 ± 1.1 kcal/mol. Combining this value with the electron affinity, 0.868 ± 0.006 eV, of the quadricyclyl radical, gives 109.4 ± 1.3 kcal/mol for the C-H bond dissociation energy of quadricyclane at C1. Reactions of quadricyclanide ion with various reagents have been studied, and branching ratios of product channels have been determined. These results, along with ab initio calculations and a companion photoelectron spectroscopy study, indicate that there are two isomers of quadricyclanide ion which have similar energies.
