The relationship between thermodynamic stabilities of carbenium ions in the gas phase and in aqueous solution: A wide scope study

The thermodynamics of the reaction R + ( g ) + R ref OH ( g ) → ROH ( g ) + R ref + ( g ) involving Rref = tert-butyl and 21 carbenium ion/alcohol systems has been studied at the MP2/6-311+G(3d, 2p)//MP2/6-311+G(d, p) level. The results have been compared to the experimental data for the same systems in solution. The range of structural effects spans 102 kcal mol−1 in the gas phase and is the widest ever examined. A physically meaningful correlation has been found. Phenyl-substituted systems are among the most important exceptions.