An EXAFS spectroscopic, large-angle X-ray scattering, and crystallographic study of hexahydrated, dimethyl sulfoxide and pyridine 1-oxide hexasolvated mercury(II) ions
(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:
https://lup.lub.lu.se/record/4332402
- author
- Persson, Ingmar ; Eriksson, Lars ; Lindqvist-Reis, Patric ; Persson, Per LU and Sandstrom, Magnus
- publishing date
- 2008
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Chemistry: A European Journal
- volume
- 14
- pages
- 6687 - 6696
- publisher
- Wiley-Blackwell
- external identifiers
-
- pmid:18563768
- scopus:53949122670
- ISSN
- 1521-3765
- DOI
- 10.1002/chem.200800225
- language
- English
- LU publication?
- no
- additional info
- 22
- id
- 485343ec-34da-4dce-a849-5c7157835ca0 (old id 4332402)
- date added to LUP
- 2016-04-01 13:00:15
- date last changed
- 2022-08-21 18:49:35
@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 = {{Wiley-Blackwell}}, 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}}, doi = {{10.1002/chem.200800225}}, volume = {{14}}, year = {{2008}}, }