Computational studies of the unusual water adduct [Cp2TiMe(OH2)](+): the roles of the solvent and the counterion.

The recently reported cationic titanocene complex [Cp2TiMe(OH2)](+) was subjected to detailed computational studies using density functional theory (DFT). The calculated NMR spectra revealed the importance of including the anion and the solvent (CD2Cl2) in order to calculate spectra which were in good agreement with the experimental data. Specifically, two organic solvent molecules were required to coordinate to the two hydrogens of the bound OH2 in order to achieve such agreement. Further elaboration of the role of the solvent led to Bader's QTAIM and natural bond order calculations. The zirconocene complex [Cp2ZrMe(OH2)](+) was simulated for comparison.