Thermochemical parameters for organic radicals and radical ions. Part 2. The protonation of hydrocarbon radicals in the gas phase

Abstract

A thermochemical cycle is used to estimate the gas phase acidity of several hydrocarbon radical cations: hydrocarbon radical cation (pKa), methane (≥ 86.5 ± 1), ethane(101 ± 1, 102 + 1), ethylene (≥ 125 ± 2), acetylene (118 ± 3, 122 ± 1), propene(124 ± 1, 122 ± 1), cyclopropane (≥ 134, ≥ 131), benzene (147 ± 1), and toluene (139 ± 1, 140). Similarly, proton affinities of the conjugate base, the hydrocarbon radical, are estimated.An estimate of the proton affinity is obtained using abinitio MO calculations. A Hartree–Fock proton affinity, PAHF(R•)g is defined as the difference in the computed energies of a radical cation and its conjugate base at the Hartree–Fock level. Calculations at the SCF level are carried out using both the minimal (STO-3G) and extended basis sets, without (3-21G, 4-31G, and 6-31G) and with (4-31G* and 6-31G*) polarization functions on carbon.The agreement between the thermochemical and abinitio estimates of the proton affinity is satisfactory.