PNNL

Abstract

Density functional theory using the zero-order regular approximate two-component relativistic Hamiltonian has been applied to calculate the 195Pt chemical shifts for the complexes [PtCl6]2-, [PtCl4]2-, and [Pt2(NH3)2Cl2((CH3)3CCONH)2- (CH2COCH3)]Cl. It is demonstrated that, in contrast to recent findings by other authors, platinum chemical shift calculations require not only a basis set beyond polarized triple-ú quality for the metal atom but also, in principle, the consideration of explicit solvent molecules in addition to a continuum model for the first two complexes. We find that the inclusion of direct solvent-solute interactions at the quantum mechanical level is important for obtaining reasonable results despite that fact that these solvent effects are rather nonspecific. The importance of solvent effects has also implications on how experimental data should be interpreted. Further, in contrast to several previous studies of heavy-metal NMR parameters, functionals beyond the local density approximation were required both in the geometry optimization and the NMR calculations to obtain reasonable agreement between the computed and experimental NMR data. This comes with the disadvantage, however, of increased Pt-ligand bond distances leading to less good agreement with experiment for structural data. A detailed analysis of the results for the two chloroplatinate complexes is presented. The same computational procedure has then been applied to the dinuclear Pt(III) complex. Chemical shifts have been calculated with respect to both [PtCl6]2- and [PtCl4]2- chosen as the NMR reference, yielding good agreement with experiment. The determination of preferred solvent locations around the complexes studied turned out to be important for reproducing experimental data.