Correlation between 195Pt chemical shifts and the electronic transitions among d orbitals in pincer NCN Pt(II) complexes: A theoretical study and application of Ramsey’s equation

• Correlation between spectral parameters and 195Pt chemical shifts in pincer NCN Pt(II) complexes.
• Correlation between chemical potentials and 195Pt chemical shifts in pincer NCN Pt(II) complexes.
• The contribution of paramagnetic part of shielding in the 195Pt chemical shifts.
• DFT was used to obtain two indices for deriving structure property relationships.

The chemical potentials for two series of [PtCl(NCN-Z-4)] (NCN = 2,6-bis[(dimethylamino)methyl]phenyl, Z = H, CHO, COOH, NH2, OH, NO2, SiMe3, I, t-Bu) and [PtCl(NCN-4-CHN-C6H4-Z′-4′)] (Z′ = NMe2, Me, H, Cl, CN) were calculated. The energies of platinum d orbitals were calculated by NBO analysis. Good correlations were obtained between 195Pt chemical shifts and the spectral parameters obtained from the energies of electronic transitions between Pt d orbitals in these complexes. The correlations between 195Pt chemical shifts and the chemical potentials were also good. The correlations were discussed based on Ramsey’s equation.

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