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An EXAFS spectroscopic, large-angle X-ray scattering, and crystallographic study of hexahydrated, dimethyl sulfoxide and pyridine 1-oxide hexasolvated mercury(II) ions

Author:
  • Ingmar Persson
  • Lars Eriksson
  • Patric Lindqvist-Reis
  • Per Persson
  • Magnus Sandstrom
Publishing year: 2008
Language: English
Pages: 6687-6696
Publication/Series: Chemistry: A European Journal
Volume: 14
Document type: Journal article
Publisher: Wiley Online Library
Additional info: 22

Abstract english

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 Hg-O 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 Hg-O distance at 2.38(1) angstrom, are surrounded by a diffuse second hydration sphere with Hg center dot center dot center dot O-II,distances of 4.20(2) angstrom. In dimethyl sulfoxide, the six Hg-O and Hg center dot center dot center dot S distances of the hexasolvated [Hg{OS(CH3)(2)}(6)](2+) complex are centered around 2.38(1) and 3.45(2) angstrom, respectively. The crystal structure of hexakis(pyridine 1-oxide)mercury(II) perchlorate has been redetermined. The space group R! implies six equal Hg-O distances of 2.3416(7) angstrom 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 Hg-O bonds according to crystallographic results, reveal in all cases strongly asymmetric Hg-O distance distributions. Vibronic coupling of valence states in a so-called pseudo-Jahn-Teller effect probably induces the distorted configurations.

Keywords

  • Earth and Related Environmental Sciences

Other

Published
  • ISSN: 1521-3765
Per Persson
E-mail: per [dot] persson [at] biol [dot] lu [dot] se

Professor

MEMEG

+46 46 222 17 96

+46 70 266 38 79

E-C350

50

Professor

Centre for Environmental and Climate Research (CEC)

+46 46 222 17 96

+46 70 266 38 79

D350

Ekologihuset, Sölvegatan 37, Lund

50