"Gas-phase-like" behavior in solution chemistry

Charge-Transfer Complexes between Dihalogen Compounds and Electron Donors

“…A set of good linear correlations between the energy of the complexes for each electron donor and those obtained in the corresponding HB complexes with HF (Figure ) is obtained: This indicates a direct relation between the ability of the electron donor to form charge-transfer complexes and their basicity in the gas phase denoted by the strength of their HB. A related experimental correlation has been described in the literature between the free energy of I 2 complexation in a series of sulfur compounds and their corresponding proton affinities in the gas phase 2 Linear correlation between the interaction energies of each series of HalB complexes and the corresponding HB ones. …”

A theoretical study of the gas phase (proton affinity) and aqueous (pKa) basicity of a series of 150 pyrazoles

“…6 Furthermore, some of us have been the main contributors to the determination of pK a (ref. 7-11) and to the gas-phase basicity of pyrazoles, both experimentally [12][13][14][15][16][17][18][19][20][21][22] and theoretically. [23][24][25][26] Therefore, we decided to carry out a theoretical study on the basicity of a large family of pyrazoles (150) for both PA and pK a (note that the collection is incomplete, only 68 PAs and 156 pK a s are reported).…”

Thermodynamic and Spectroscopic Scales of Halogen‐Bond Basicity and Affinity

“…However, linear Gibbs energy relationships of good precision were found [84] for families of structurally related bases. It was not possible to find a general relationship between the K c values determined in these two solvents.…”