The crystal structure of potassium tetranitrohydroxynitrosoruthenia te K2[RuNO(OH)(NO2)4]

Bokii, G. B.; Ang-nu, Wang; Khodashova, T. S.

doi:10.1007/bf00746134

Cited by 7 publications

(4 citation statements)

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“…On the contrary, for a smaller angle it is Ru 3+ -NO, meaning that this angle is an indicator of the Ru-NO bond strength. 26,27 The presence of a hydroxide ion, a strong electron donor, in the trans position weakens the Ru-NO bond.…”

Section: Resultsmentioning

confidence: 99%

“…According to the literature, when the Ru-NO group is linear (angle = 180°), the complex can be considered as Ru 2+ -NO + . On the contrary, for a smaller angle it is Ru 3+ -NO, meaning that this angle is an indicator of the Ru-NO bond strength. , The presence of a hydroxide ion, a strong electron donor, in the trans position weakens the Ru-NO bond.…”

Section: Resultsmentioning

confidence: 99%

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Addressing Ruthenium Speciation in Tri-n-butyl-phosphate Solvent Extraction Process by Fourier Transform Infrared, Extended X-ray Absorption Fine Structure, and Single Crystal X-ray Diffraction

Lefebvre

Dumas

Tamain

et al. 2017

Ind. Eng. Chem. Res.

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In industrial nuclear fuel reprocessing, small amounts of ruthenium are extracted by tri-n-butyl-phosphate (TBP) at the same time as uranium and plutonium. This behavior increases solvent radiolysis and requires secondary extraction cycles to minimize the residual ruthenium content in uranium and plutonium products. However, the solvent ruthenium extraction mechanism remains largely unexplored. This study addresses the speciation of ruthenium in solvent extraction conditions by complementary infrared and X-ray absorption spectroscopy. First, spectroscopic result interpretation is supported by a single crystal X-ray diffraction study on reference compounds to unambiguously demonstrate that the ruthenium extraction mechanism is driven by a weak outer-sphere Ru–TBP interaction. Second, the ruthenium coordination sphere is quantitatively characterized. Ruthenium speciation in the organic phase depends on the initial aqueous phase, and both monomeric ruthenium nitrosyl trinitrate complexes and a hydrolyzed dimeric ruthenium nitrosyl complex are shown. Average coordination numbers for nitrate, hydroxide, and aquo ligands are accurately determined in both phases, by applying a constrained EXAFS fit approach.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Addressing Ruthenium Speciation in Tri-n-butyl-phosphate Solvent Extraction Process by Fourier Transform Infrared, Extended X-ray Absorption Fine Structure, and Single Crystal X-ray Diffraction

Lefebvre

Dumas

Tamain

et al. 2017

Ind. Eng. Chem. Res.

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“…During PUREX extraction cycles, extractable ruthenium appears in the form of numerous nitrosyl (RuNO) complexes. ,, These complexes have a pseudo-octahedral geometry, in which the Ru–NO bond is shorter than the ones to the other five ligands . Siczek and Steindler have published a general formula to summarize the general diversity of RuNO complexes in nitric acid solution: Nitrates, nitrites, and water ligands can occupy the equatorial position of the octahedral complexes, whereas one water or one hydroxide ligand occupies the axial position in opposite to the nitrosyl ligand .…”

Section: Introductionmentioning

confidence: 99%

Ruthenium Nitrosyl Structure in Solvent Extraction Systems: A Comparison of Tributyl Phosphate, Tetrabutyl Urea, N-Methyl, N-Octyl Ethylhexanamide, and N,N,N′,N′-Tetraoctyl Diglycolamide

Dirks

Dumas

Solari

et al. 2019

Ind. Eng. Chem. Res.

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In the course of nuclear fuel treatment, solvent extraction cycles separate uranium and plutonium from fission products and minor actinides. During these steps, small amounts of the fission product ruthenium may follow the uranium and plutonium products. Herein, we show by Raman spectroscopy how ruthenium complexes in the aqueous phase differ as a function of the nitric acid concentration. Furthermore, we compare ruthenium extraction by the industrially used solvent tri-n-butylphosphate to other extractants such as tetrabutyl urea, N-methyl, N-octyl ethylhexanamide, and N,N,N′,N′-tetraoctyl diglycolamide. Analysis by inductively coupled plasma atomic emission spectroscopy demonstrates that all of these solvents have different ruthenium distribution ratios. In contrast, similar ruthenium complexes were identified by Fourier transform infrared and extended X-ray absorption fine structure spectroscopy in all extractions from 4 M nitric acid. Hence, different distribution ratios of ruthenium are not due to different ruthenium complexes. By comparing ruthenium extraction with nitric acid and water extraction, we show a linear correlation between ruthenium and water concentration in the organic phase. This suggests an interaction between the solvent and water ligands during ruthenium extraction. To limit the ruthenium coextraction in nuclear fuel treatments, we suggest further investigation of solvents with low water coextraction.

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“…(5) However, there were some details in the structure of (c) and (d), especially the Ru-N-O bonding, that made it desirable to examine a similar type of compound, particularly in view o£ the current interest in ruthenium, nitrosyl complexes. Also, all the previous structures had been solved by projections and the more accurate bond lengths attainable from three-dimensional data were desired.…”

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confidence: 99%

THE CRYSTAL STRUCTURE OF DISODIUM TETRANITRITONITROSOHYDROXYRUTHENATE(III) 2-HYDRATE BY NEUTRON DIFFRACTION. Final Report--Program 4.10.22

Mueller¹,

Simonsen²

1964

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The crystal structure of potassium tetranitrohydroxynitrosoruthenia te K2[RuNO(OH)(NO2)4]

Cited by 7 publications

References 1 publication

Addressing Ruthenium Speciation in Tri-n-butyl-phosphate Solvent Extraction Process by Fourier Transform Infrared, Extended X-ray Absorption Fine Structure, and Single Crystal X-ray Diffraction

Addressing Ruthenium Speciation in Tri-n-butyl-phosphate Solvent Extraction Process by Fourier Transform Infrared, Extended X-ray Absorption Fine Structure, and Single Crystal X-ray Diffraction

Ruthenium Nitrosyl Structure in Solvent Extraction Systems: A Comparison of Tributyl Phosphate, Tetrabutyl Urea, N-Methyl, N-Octyl Ethylhexanamide, and N,N,N′,N′-Tetraoctyl Diglycolamide

THE CRYSTAL STRUCTURE OF DISODIUM TETRANITRITONITROSOHYDROXYRUTHENATE(III) 2-HYDRATE BY NEUTRON DIFFRACTION. Final Report--Program 4.10.22

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