Structure of the Solvated Zinc(II), Cadmium(II), and Mercury(II) Ions in<i>N</i>,<i>N</i>-Dimethylthioformamide Solution

Stålhandske, Claes; Persson, Ingmar; Sandström, Magnus; Kamieńska-Piotrowicz, Ewa

doi:10.1021/ic961339i

Cited by 66 publications

(120 citation statements)

References 39 publications

(75 reference statements)

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“…54 The solution was contained in a Teflon cup filled until a positive meniscus was observed generating a flat surface in the irradiated region. The container was placed inside an air-tight radiation shield with beryllium windows.…”

Section: Large Angle X-ray Scatteringmentioning

confidence: 99%

Hydration of arsenic oxyacid species

2013

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The bond distances in hydrated arsenic oxyacid species in aqueous solution have been studied by EXAFS spectroscopy and large angle X-ray scattering, LAXS. These results have been compared to structures in the solid state, as found in an extensive survey of available crystal structures. Protonated oxygen atoms can be distinguished with a longer As-O distance for both arsenic(V) and arsenic(III) species in the crystalline state. However, the average As-O distance for the H n AsO 4 (3-n)-species (0 ≤ n ≤3) remains the same. These average values are slightly shorter, ca. 0.02 Å, than in aqueous solution due to the hydration as determined by EXAFS and LAXS. The K absorption edges for arsenic(V) and arsenic(III) species are separated by 4.0 eV, and the shape of the absorption edges differs as well. Small but significant differences in the absorption edge features are seen between the neutral acids and the charged oxyacid species. The most important arsenic species from an environmental point of view is arsenous acid, As(OH) 3 . Arsenous acid cannot be studied with the same accuracy as orthotelluric acid, due to a relatively low solubility of As 2 O 3 (s) in neutral to acidic aqueous solution. In addition to arsenous acid, we have used orthotelluric acid, Te(OH) 6 , for comparison with arsenous acid and for detailed studies of the hydration of covalently bound hydroxo groups. The results from the DDIR studies support the assignment of As(OH) 3 as a weak structure maker analogous to Te(OH) 6 , both being neutral weak oxyacids.

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Section: Large Angle X-ray Scatteringmentioning

confidence: 99%

Hydration of arsenic oxyacid species

2013

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“…[9,10] Di-and tridentate sulfur-donor ligands are required to form six-coordinated mercury(II) complexes. [11][12][13] The destabilization of regular six-coordinated mercury(II) complexes, including small monodentate ligands, such as ammonia, is often attributed to a contribution of the mercury(II) 5d z 2 atomic orbital to the bonding molecular orbitals by vibronic coupling of pseudo-degenerate electronic states in a socalled pseudo-Jahn-Teller effect (PJTE).…”

Section: Introductionmentioning

confidence: 99%

An EXAFS Spectroscopic, Large‐Angle X‐Ray Scattering, and Crystallographic Study of Hexahydrated, Dimethyl Sulfoxide and Pyridine 1‐Oxide Hexasolvated Mercury(II) Ions

Persson

Eriksson

Lindqvist‐Reis

et al. 2008

Chemistry A European J

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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(OH(2))(6)](2+) ions in a distorted octahedral configuration, with the centroid of the Hg-O distance at 2.38(1) A, are surrounded by a diffuse second hydration sphere with HgO(II) distances of 4.20(2) A. In dimethyl sulfoxide, the six Hg-O and HgS distances of the hexasolvated [Hg{OS(CH(3))(2)}(6)](2+) complex are centered around 2.38(1) and 3.45(2) A, respectively. The crystal structure of hexakis(pyridine 1-oxide)mercury(II) perchlorate has been redetermined. The space group R(-)3 implies six equal Hg-O distances of 2.3416(7) A for the [Hg(ONC(5)H(5))(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.

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“…10 A flat measuring surface of the irradiated area was obtain by filling a Teflon cup until a positive meniscus was observed and sealing it in an airtight measuring chamber with beryllium windows. A LiF(200) single crystal focusing monochromator was used to monochromatize the scattered radiation.…”

Section: Large Angle X-ray Scattering (Laxs)mentioning

confidence: 99%

“…The details of data collection and treatment are described elsewhere. 10 The KURVLR software 11 was used for the data treatment, The structural parameters contained in the theoretical model where refined by minimizing U = w(s)Σs 2 [i exp (s)-i calc (s)]² using the STEPLR program. 12,13 Normalization of the data to one stoichiometric unit containing two sulfur atoms using the scattering factors f for neutral atoms, including corrections for anomalous dispersion, Δf' and Δf'', 14 Compton scattering 15,16 and multiple scattering events.…”

Section: Large Angle X-ray Scattering (Laxs)mentioning

confidence: 99%

Structure and water exchange of the hydrated thiosulfate ion in aqueous solution using QMCF MD simulation and large angle X-ray scattering

et al. 2014

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, x=3-8, and radial distribution functions from simulation of the thiosulfate ion, and from experimental LAXS data on the hydrated peroxodisulfate ion in water. Graphical Abstract SynopsisExperimental and simulation data of the thiosulfate ion show large similarities in hydration structure and mechanism with the sulfate ion but with weaker hydration of the terminal sulfur atom in thiosulfate. AbstractTheoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) to study the structure and dynamics of the hydrated thiosulfate ion, S 2 O 3 2-, in aqueous solution. The S-O and S C -S T bond distances have been determined to 1.479(5) and 2.020(6) Å by LAXS and to 1.478 and 2.017 Å by QMCF MD simulations, which are slightly longer than the mean values found in the solid state, 1.467 and 2.002 Å, respectively. This is due to the hydrogen bonds formed at hydration.The water dynamics show that water molecules are exchanged at the hydrated oxygen and sulfur atoms, and that the water exchange is ca. 50% faster at the sulfur atom than at the oxygens atoms with mean residence times,  0.5 , of 2.4 and 3.6 ps, respectively. From this point of view the water exchange dynamics mechanism resembles the sulfate ion, while it is significantly different from the sulfite ion. This shows that the lone electron-pair in the sulfite ion has a much larger impact on the water exchange dynamics than a substitution of an oxygen atom for a sulfur one. The LAXS data did give mean S C ⋅⋅⋅O aq1 and S C ⋅⋅⋅O aq2 distances of 3.66(2) and 4.36(10) Å, respectively, and S C -O thio and O thio ⋅⋅⋅O aq1 , S C -S T and S T ⋅⋅⋅O aq2 distances of 1.479(5), 2.845(10), 2.020(6) and 3.24(5) Å, respectively, giving S C -O thio ⋅⋅⋅O aq1 and S C -S T ⋅⋅⋅O aq2 angles close 110 o , strongly indicating a tetrahedral geometry around the terminal thiosulfate sulfur and the oxygens, and thereby, three water molecules are hydrogen bound to each of them. The hydrogen bonds between thiosulfate oxygens and the hydrating water molecules are stronger and with longer mean residence times than between water molecules in the aqueous bulk, while the opposite is true for the hydrogen bonds between the terminal thiosulfate sulfur and the hydrating water molecules. The hydration of all oxo sulfur ions are discussed using the detailed observations for the sulfate, thiosulfate and sulfite ions, and the structure of the hydrated peroxodisulfate ion, S 2 O 8 2-, in aqueous solution has been determined by means of LAXS to support the general observations. The mean S-O bond distances are 1.448(2) and 1.675(5) Å to the oxo and peroxo oxygens, respectively.

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Structure of the Solvated Zinc(II), Cadmium(II), and Mercury(II) Ions inN,N-Dimethylthioformamide Solution

Cited by 66 publications

References 39 publications

Hydration of arsenic oxyacid species

Hydration of arsenic oxyacid species

An EXAFS Spectroscopic, Large‐Angle X‐Ray Scattering, and Crystallographic Study of Hexahydrated, Dimethyl Sulfoxide and Pyridine 1‐Oxide Hexasolvated Mercury(II) Ions

Structure and water exchange of the hydrated thiosulfate ion in aqueous solution using QMCF MD simulation and large angle X-ray scattering

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