A DFT study on the interactions between the [Pt(H2O)(terpy)]2+ cation and the triflate and perchlorate counter-anions

The results of DFT B3PW91 calculations on the [(terpy)Pt(OH2⋯X)]+ and [(terpy)Pt(OH2⋯S)]2+ {terpy = 2,2′:6′,2″-terpyridine; X = ClO4, SO3CF3; S = CH3NO2} models, carried out in order to evaluate the different interaction energy of the [Pt(H2O)(terpy)]2+ cation with SO3CF3- and ClO4- counter-anions, as well as with nitromethane, are reported. The computational results likely fit the previously reported X-ray and NMR data on the [Pt(H2O)(terpy)]X2 {X = ClO4, SO3CF3} species [G. Annibale, P. Bergamini, V. Bertolasi, M. Bortoluzzi, M. Cattabriga, B. Pitteri, Eur. J. Inorg. Chem. (2007) 5743].

Graphical abstractThe results of DFT calculations on the [Pt(OH2⋯X)(terpy)]+ and [Pt(OH2⋯S)(terpy)]2+ {terpy = 2,2′:6′,2″-terpyridine; X = ClO4, SO3CF3; S = CH3NO2} models are reported. The computational results likely fit the previously reported X-ray and NMR data on the [Pt(H2O)(terpy)]X2 {X = ClO4, SO3CF3} species and allowed to estimate the energy difference between the [(terpy)Pt–OH2⋯OSO2CF3]+ and the [(terpy)Pt–OH2⋯OClO3]+ hydrogen-bond adducts. Finally, it was highlighted that also nitromethane is able to strongly interact with the aqua ligand of the [Pt(H2O)(terpy)]2+ cation.Figure optionsDownload full-size imageDownload as PowerPoint slide