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An EXAFS Spectroscopic, Large Angle X-Ray Scattering and Crystallo¬graphic Study of the Hexahydrated and the Dimethyl Sulfoxide and Pyridine-1-Oxide Hexasolvated Mercury(II) Ions
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
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2008 (English)In: Chemistry, A European Journal, Vol. 14, 6687-6696 p.Article in journal (Other (popular science, discussion, etc.)) Published
Abstract [en]

The structure of the solvated mercury(II) ion in aqueous and dimethyl sulfoxide solution has been studied by means of large angle X-ray scattering (LAXS) and EXAFS tech¬niques. The distribution of the Hg-O bond distances is unusually wide and asymmetric in both solvents. In aqueous solution hexahydrated [Hg(OH2)6]2+ ions in distorted octahedral configuration, with the centroid of the Hg-O bond distances at 2.38(1) Å, are surrounded by a diffuse second hydration sphere, with HgOII distances around a mean value of 4.20(2) Å. In dimethyl sulfoxide solution the six Hg-O and HgS 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 re-determi¬ned at 100 K. The space group R implies six equal Hg-O bond distances of 2.3416(7) Å for the Hg(ONC5H5)62+ complex, as also for the hexaaquamercury(II) perchlorate and hexakis(dimethyl sulfoxide)mercury(II) trifluoro¬methanesulfonate compounds, according to previous crystallographic results. However, EXAFS results for those compounds in all cases reveal strongly asymmetric Hg-O bond distance distributions. Vibronic coupling of close valence states in a so-called Pseudo Jahn-Teller Effect probably induces the distorted configurations.

Place, publisher, year, edition, pages
2008. Vol. 14, 6687-6696 p.
Keyword [en]
Mercury(II) solvation, EXAFS spectroscopy, X-ray diffraction, solution structure
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-14876ISI: 000258217000016OAI: oai:DiVA.org:su-14876DiVA: diva2:181396
Available from: 2008-11-06 Created: 2008-11-06 Last updated: 2011-01-10Bibliographically approved

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Eriksson, LarsSandström, Magnus
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