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

Spectrochim Acta A Mol Biomol Spectrosc. 2015 Dec 5:151:438-42. doi: 10.1016/j.saa.2015.06.122. Epub 2015 Jun 30.

Abstract

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 (195)Pt chemical shifts and the spectral parameters obtained from the energies of electronic transitions between Pt d orbitals in these complexes. The correlations between (195)Pt chemical shifts and the chemical potentials were also good. The correlations were discussed based on Ramsey's equation.

Keywords: Density functional calculations; Organoplatinum(II) complexes; Paramagnetic shielding; Ramsey’s equation.

Publication types

  • Research Support, Non-U.S. Gov't