Electrochemistry of molybdenum chloride dimers in a basic ambient-temperature molten salt

Carlin, Richard T.; Osteryoung, R. A.

doi:10.1021/ic00281a034

Cited by 19 publications

(10 citation statements)

References 2 publications

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“…Acidic melts also yield electrochemical data that suggests the presence of single cluster species wherein the [(Nb,Ta) 6 Cl 12 ] n+ cluster cores are perhaps weakly ligated by AlCl 4ions, though extent of such ligation is unclear. AlCl 3 -ImCl ionic liquids have shown their usefulness in the electrochemical study of several other well-known inorganic cluster systems, including [Mo 2 Cl 8 ] 4-, 20 [(Mo 6 Cl 8 )Cl 6 ] 2-, 21 [Re 2 Cl 8 ] 2-, 22 [Re 2 Cl 8 ] 3-, 23 [Re 3 Cl 12 ] 3-, 22 and [W 2 Cl 9 ] 3-. 24 We have demonstrated that ambient-temperature ionic liquids are useful solvents for excising hexanuclear zirconium halide clusters from solid-state precursors 11,13,25,26 and we therefore viewed them as desirable media for electrochemical investigation of these clusters.…”

Section: Introductionmentioning

confidence: 99%

Electrochemistry of Centered Hexanuclear Zirconium Halide Clusters in Ambient-Temperature Chloroaluminate Molten Salts

Sun

Hughbanks

1999

Inorg. Chem.

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Ambient temperature AlCl(3)-1-ethyl-3-methylimidazolium chloride (ImCl) molten salts, both basic (40/60 mol % AlCl(3)/ImCl) and acidic (60/40 mol % AlCl(3)/ImCl), were used in an electrochemical investigation of centered hexanuclear zirconium halide clusters. In the basic molten salt, these [(Zr(6)ZCl(12))Cl(6)](n-) (Z = Be, B, C, Mn, Fe) centered clusters exhibit the following electrochemical reactions on a glassy carbon electrode (potentials vs Al/Al(3+)): [(Zr(6)BeCl(12))Cl(6)](n)()(-) + e(-) right harpoon over left harpoon [(Zr(6)BeCl(12))Cl(6)](()(n)()(+1))(-), E(1/2) = -0.613 V (n = 4), E(1/2) = -1.085 V (n = 5); [(Zr(6)BCl(12))Cl(6)](n)()(-) + e(-) right harpoon over left harpoon [(Zr(6)BCl(12))Cl(6)](()(n)()(+1))(-), E(1/2) = -0.365 V (n = 4), E(1/2) = 0.072 V (n = 3); [(Zr(6)CCl(12))Cl(6)](n)()(-) + e(-) right harpoon over left harpoon [(Zr(6)CCl(12))Cl(6)](()(n)()(+1))(-), E(1/2) = 0.230 V (n = 3); [(Zr(6)MnCl(12))Cl(6)](4)(-) + e(-) right harpoon over left harpoon [(Zr(6)MnCl(12))Cl(6)](5)(-), E(1/2) = -0.432 V. In the acidic melt, only electrochemical reactions [(Zr(6)BeCl(12))(AlCl(4))(6)](n)()(-) + e(-) right harpoon over left harpoon [(Zr(6)BeCl(12))(AlCl(4))(6)](()(n)()(+1))(-), E(1/2) = -0.069 V (n = 5), E(1/2) = 0.504 V (n = 4), and [(Zr(6)BCl(12))(AlCl(4))(6)](4)(-) + e(-) right harpoon over left harpoon [(Zr(6)BCl(12))(AlCl(4))(6)](5)(-), E(1/2) = 0.700 V are clearly observed. These data is consistent with less systematic observations of oxidation of these clusters in solution. No unambiguous one-electron electrochemical reduction nor oxidation is observable for the Fe-centered cluster in the ionic liquids. The half-wave potentials of the above reactions of the Be-, B-, C-, and Mn-centered clusters are controlled largely by clusters' charges. This correlation of redox potentials allows a useful direct comparison with data for related hexanuclear niobium clusters in the literature.

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Section: Introductionmentioning

confidence: 99%

Electrochemistry of Centered Hexanuclear Zirconium Halide Clusters in Ambient-Temperature Chloroaluminate Molten Salts

Sun

Hughbanks

1999

Inorg. Chem.

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“…Of all the alkali chloride mixtures used in the present work LiCl-KCl eutectic has the smallest mean cationic radius and thus will have greatest polarizing effect on MoCl 6 -complex ions. As a rule, transition metal chloride complexes are least stable in lithium chloride containing melts; destabilization of the complex ion in our case should shift the equilibrium [1] to the formation of MoCl 5 .…”

Section: Resultsmentioning

confidence: 65%

“…15500 cm -1 that corresponds very closely to the position of the high-energy band in the spectra of molybdenum pentachloride solutions in alkali chloride melts. Therefore it is very likely that the high energy constituent band appearing at higher temperatures in the absorption spectra of Mo(V) in fused chlorides results from the absorption of dissolved molecular MoCl 5 formed as a result of shifting equilibrium [1] to the right.…”

Section: Resultsmentioning

confidence: 99%

Molybdenum(V) Species in Alkali Chloride Melts: An Electronic Absorption Spectroscopy Study

et al. 2014

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Electronic absorption spectra of solutions of molybdenum pentachloride in fused alkali chlorides were studied between 450 and 850 oC. LiCl-KCl, NaCl-CsCl, NaCl-KCl-CsCl eutectics and NaCl-KCl equimolar mixture were used as solvents. Although the experimental spectra contain only one broad band in the visible region, resolving the spectra into overlapping bands revealed two individual components under the experimental band. The ratio of intensities of the constituent bands depends on temperature and they are attributed to the absorption of MoCl6 - ion and MoCl5 molecular species. Spectroscopic parameters of MoCl6 - were determined and MoCl6 -↔MoCl5 equilibrium is discussed. Absorption spectra of gaseous MoCl5 were also recorded.

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“…The formation of Mo(IV) chloro-species in ionic media was noted in low temperature ionic liquids and in alkali chloride melts, but only recently has the existence of MoCl 6 2-species in molten chlorides been confirmed (12,(18)(19)(20). Of the lower oxidation state (below three) molybdenum species, only dimeric molybdenum(II) complexes have been characterized in low temperature ionic liquids (21,22). There are no reliable data confirming the existence of such species in high temperature melts.…”

Section: Introductionmentioning

confidence: 99%

Behavior of Molybdenum Chloro-Species in Alkali Chloride-Based Melts: Implications for Spent Nuclear Fuel Treatments

Volkovich¹,

Polovov²,

Камалов³

et al. 2010

ECS Trans.

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Chloro-species of molybdenum in oxidation states (III), (IV) and (V) were studied in a range of alkali chloride melts employing high temperature electronic absorption spectroscopy. The reaction rates of disproportionation of MoCl63- complex ions in various melts between 550 and 750 oC were determined. Mo(IV) species MoCl62- were generated and thermodynamic properties of Mo(IV) chloride in NaCl-CsCl eutectic melt estimated. Absorption spectra of molybdenum(V) MoCl6- were measured in a chloride melt for the first time. Speciation and behavior of molybdenum is required for designing processes for molten salt reprocessing of spent nuclear fuel (SNF).

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Electrochemistry of molybdenum chloride dimers in a basic ambient-temperature molten salt

Cited by 19 publications

References 2 publications

Electrochemistry of Centered Hexanuclear Zirconium Halide Clusters in Ambient-Temperature Chloroaluminate Molten Salts

Electrochemistry of Centered Hexanuclear Zirconium Halide Clusters in Ambient-Temperature Chloroaluminate Molten Salts

Molybdenum(V) Species in Alkali Chloride Melts: An Electronic Absorption Spectroscopy Study

Behavior of Molybdenum Chloro-Species in Alkali Chloride-Based Melts: Implications for Spent Nuclear Fuel Treatments

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