Advanced

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

Persson, Ingmar; Eriksson, Lars; Lindqvist-Reis, Patric; Persson, Per LU and Sandstrom, Magnus (2008) In Chemistry: A European Journal 14. p.6687-6696
Abstract
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... (More)
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. (Less)
Please use this url to cite or link to this publication:
author
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemistry: A European Journal
volume
14
pages
6687 - 6696
publisher
John Wiley & Sons
external identifiers
  • scopus:53749090791
ISSN
1521-3765
DOI
10.1002/chem.200800225
language
English
LU publication?
no
id
485343ec-34da-4dce-a849-5c7157835ca0 (old id 4332402)
date added to LUP
2014-03-04 09:47:19
date last changed
2017-01-01 05:24:49
@article{485343ec-34da-4dce-a849-5c7157835ca0,
  abstract     = {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.},
  author       = {Persson, Ingmar and Eriksson, Lars and Lindqvist-Reis, Patric and Persson, Per and Sandstrom, Magnus},
  issn         = {1521-3765},
  language     = {eng},
  pages        = {6687--6696},
  publisher    = {John Wiley & Sons},
  series       = {Chemistry: A European Journal},
  title        = {An EXAFS spectroscopic, large-angle X-ray scattering, and crystallographic study of hexahydrated, dimethyl sulfoxide and pyridine 1-oxide hexasolvated mercury(II) ions},
  url          = {http://dx.doi.org/10.1002/chem.200800225},
  volume       = {14},
  year         = {2008},
}