Assessment of theoretical prediction of the NMR shielding tensor of 195PtClxBr6−x2− complexes by DFT calculations: experimental and computational results

Abstract

In the present work, the ZORA spin–orbit Hamiltonian, in conjunction with the gauge including orbital (GIAO) method based on DFT theory has been used to calculate ¹⁹⁵Pt chemical shift of ¹⁹⁵PtCl_xBr_6−x²⁻ complexes. Excellent agreement with experiments has been obtained for calculations bearing on optimized geometries and all electrons triple zeta + polarization (TZP) STO basis sets: the relative error with respect to experiment amounts to <1.5%. It is found that the Pt chemical shift is dominated by the paramagnetic and the spin orbit contribution, whereas the diamagnetic term remains negligible. The influence of the quality of the basis sets has been studied and found to be small, provided a basis set like TZP is used. Several calculations have been performed in order to establish the sensitivity of the chemical shift to a variation in the bond lengths. A strong dependence has been found, with an increase of the chemical shift amounting to 150 ppm pm⁻¹ for a distance decrease. Large sensitivity to the solvation, leading to changes in the structure, is then expected. Different tests using conductor-like screening models have been performed in order to establish the sensitivity of the chemical shift to solvation. It has been observed that the changes in the geometry are more important than charge transfers. Finally, the sensitivity of the system to the exchange–correlation functional is found rather weak, at least among the GGA functionals.