Change search
ReferencesLink to record
Permanent link

Direct link
An EXAFS Spectroscopic, Large-Angle X-Ray Scattering, and Crystallographic Study of Hexahydrated, Dimethyl Sulfoxide and Pyridine 1-Oxide Hexasolvated Mercury(II) Ions
Umeå University, Faculty of Science and Technology, Chemistry.
Show others and affiliations
2008 (English)In: Chemistry - A European Journal, Vol. 14, no 22, 6687-96 p.Article in journal (Refereed) Published
Abstract [en]

The structure of the solvated mercury(II) ion in water and dimethyl sulfoxide has been studied by means of large-angle X-ray scattering (LAXS) and extended X-ray absorption fine structure (EXAFS) techniques. The distribution of the HgO distances is unusually wide and asymmetric in both solvents. In aqueous solution, hexahydrated [Hg(OH2)6]2+ ions in a distorted octahedral configuration, with the centroid of the HgO distance at 2.38(1) Å, are surrounded by a diffuse second hydration sphere with HgOII distances of 4.20(2) Å. In dimethyl sulfoxide, the six HgO and HgS distances of the hexasolvated [Hg{OS(CH3)2}6]2+ complex are centered around 2.38(1) and 3.45(2) Å, respectively. The crystal structure of hexakis(pyridine 1-oxide)mercury(II) perchlorate has been redetermined. The space group R3¯ implies six equal HgO distances of 2.3416(7) Å for the [Hg(ONC5H5)6]2+ complex at 100 K. However, EXAFS studies of this compound, and of the solids hexaaquamercury(II) perchlorate and hexakis(dimethyl sulfoxide)mercury(II) trifluoromethanesulfonate, also with six equidistant HgO bonds according to crystallographic results, reveal in all cases strongly asymmetric HgO distance distributions. Vibronic coupling of valence states in a so-called pseudo-Jahn-Teller effect probably induces the distorted configurations.

Place, publisher, year, edition, pages
2008. Vol. 14, no 22, 6687-96 p.
Keyword [en]
dimethyl sulfoxide, hydrates, Jahn-Teller distortion, mercury, structure elucidation
URN: urn:nbn:se:umu:diva-10146DOI: doi:10.1002/chem.200800225OAI: diva2:149817
Published Online 18 June 2008Available from: 2008-08-05 Created: 2008-08-05 Last updated: 2011-01-10Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Persson, Per
By organisation

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 26 hits
ReferencesLink to record
Permanent link

Direct link