A semi-empirical structural-thermochemical approach was employed to study the vaporization properties of new molecular titanium coordination compounds. Examination of intramolecular steric shielding of individual atoms, and analysis of intermolecular close contacts, identified which groups of atoms in the molecules were important. Evaporation enthalpies were calculated by summing the contributions from the individual groups. Addition of the measured melting enthalpies gave sublimation enthalpies agreeing closely with data determined experimentally using high temperature mass spectrometry.