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The solvation of the mercury(II) ion—a 199 Hg NMR study
Author(s) -
Maliarik Mikhail,
Persson Ingmar
Publication year - 2005
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1625
Subject(s) - chemistry , solvation , chemical shift , octahedron , ion , mercury (programming language) , kinetic isotope effect , anisotropy , inorganic chemistry , crystallography , deuterium , organic chemistry , atomic physics , computer science , programming language , physics , quantum mechanics
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. Copyright © 2005 John Wiley & Sons, Ltd.