The solvation of the mercury(II) ion-a 199Hg NMR study.
The solvation of the mercury(II) ion in solvents with different solvation properties, water, dimethylsulfoxide, N,N-dimethylthioformamide, and liquid ammonia, has been studied by means of (199)Hg NMR. The (199)Hg chemical shift shows a pronounced dependence on the coordination number of the mercury(II) ion in the solvates resulting in a difference of over 1200 ppm between basically tetrahedral and octahedral complexes. The chemical shifts can furthermore be associated with electron-pair donor properties of the solvents. The spin-lattice relaxation times of the (199)Hg nucleus in the solvates have been measured at different applied magnetic fields, concentrations, temperatures, and isotope substitutions. Possible mechanisms for the (199)Hg relaxation were proposed and the chemical shielding anisotropy in the solvates has been estimated. The (199)Hg relaxation rates and the anisotropy are correlated with the structure of the solvate complexes in solution obtained from recent LAXS and EXAFS studies.
Maliarik
Mikhail
M
IFM-Department of Chemistry, Linköping University, S-581 83 Linköping, Sweden. misha@ifm.liu.se
Persson
Ingmar
I
D016880:Anisotropy; D009682:Magnetic Resonance Spectroscopy / Q000379:methods* / Q000592:standards; D008628:Mercury / Q000737:chemistry*; D008629:Mercury Isotopes; D012015:Reference Standards; D012995:Solubility; D012997:Solvents / Q000737:chemistry; D013696:Temperature
D008629:Mercury Isotopes; D012997:Solvents; D008628:Mercury