Spectroscopic characterization of the octachlorodirhenate(3-) ion, [Re2Cl8]3-

Strubinger, Sandra K. D.; Hussey, Charles L.; Cleland, W. E.

doi:10.1021/ic00022a033

Cited by 11 publications

(4 citation statements)

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“…Notably, Δ has been examined for a number of (δ,δ*) 1 and (δ,δ*) 3 complexes containing Mo 2 5+ , Tc 2 5+ , Re 2 5+ , and W 2 5+ bimetallic centers . Complexes bearing π-donating equatorial ligands, such as halides, exhibit δ → δ* transitions between 6500 and 7600 cm –1 . ,− Complexes with equatorial O -donor ligands (e.g., carboxylates) have Δ values of 14 500–18 200 cm –1 , , and those with N -donor ligands are similar (∼14 900 cm –1 ) . In comparison, the δ → δ* transitions for Ru 2 5+ carboxylate complexes have been observed at ∼1100 nm, yielding Δ ≈ 9000 cm –1 .…”

Section: Resultsmentioning

confidence: 99%

Electronic Structure of Anilinopyridinate-Supported Ru₂⁵⁺ Paddlewheel Compounds

et al. 2017

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The electronic structures of the diruthenium compounds Ru(ap)Cl (1, ap = 2-anilinopyridinate) and Ru(ap)OTf (2) were investigated with UV-vis, resonance Raman, and magnetic circular dichroism (MCD) spectroscopies; SQUID magnetometry; and density functional theory (DFT) calculations. Both compounds have quartet spin ground states with large axial zero-field splitting of ∼60 cm that is characteristic of Ru compounds having a (π*, δ*) electron configuration and a Ru-Ru bond order of ∼2.5. Two major visible absorption features are observed at ∼770 and 430 nm in the electronic spectra, the assignments of which have previously been ambiguous. Both bands have significant charge-transfer character with some contributions from d → d transitions. MCD spectra were measured to enable the identification of d → d transitions that are not easily observable by UV-vis spectroscopy. In this way, we are able to identify bands due to δ → δ* and δ → π* transitions at ∼16 100 and 11 200-12 300 cm, respectively, the latter band being sensitive to the π-donating character of the axial ligand. The Ru-Ru stretches are coupled with pyridine rocking motions and give rise to observed resonance Raman peaks at ∼350 and 420 cm, respectively.

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Section: Resultsmentioning

confidence: 99%

Electronic Structure of Anilinopyridinate-Supported Ru₂⁵⁺ Paddlewheel Compounds

et al. 2017

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“…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- , [(Mo 6 Cl 8 )Cl 6 ] 2- , [Re 2 Cl 8 ] 2- , [Re 2 Cl 8 ] 3- , [Re 3 Cl 12 ] 3- , and [W 2 Cl 9 ] 3- . We have demonstrated that ambient-temperature ionic liquids are useful solvents for excising hexanuclear zirconium halide clusters from solid-state precursors ,,, and we therefore viewed them as desirable media for electrochemical investigation of these clusters.…”

Section: Introductionmentioning

confidence: 90%

“…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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“…Subsequent spectroscopic studies of rhenium in chloride systems have been mainly limited to the low-temperature ionic systems. Strubinger et al [22][23][24] have investigated rhenium(III) and (IV) species in room temperature were also reported in AlCl 3 -NaCl melts at 175 C. 25 In all the above work rhenium was introduced into the melts by dissolving various rhenium chloride salts, so there was no information on the formation of rhenium chlorides from other starting compounds, e.g., metal or oxides. Spectroscopic properties of technetium in molten salt systems (either high-or low-temperature) have not been previously reported.…”

Section: Introductionmentioning

confidence: 99%

Reactions and speciation of technetium and rhenium in chloride melts: a spectroscopy study

Volkovich

May

Charnock

et al. 2002

Phys. Chem. Chem. Phys.

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The reactions of rhenium metal, rhenium oxides (ReO 2 and ReO 3 ) and technetium dioxide with chlorine and hydrogen chloride were investigated in LiCl-KCl, NaCl-CsCl and NaCl-KCl based melts between 450 and 720 C. Reaction progress was followed using in situ electronic absorption spectroscopy, with the spectra measured between 200 and 1100 nm. Samples of the quenched melts were analysed by EXAFS spectroscopy. Rhenium metal and rhenium oxides react with Cl 2 or HCl yielding hexachlororhenate(IV) species, although the reaction of rhenium metal with HCl is extremely slow even at 700 C and no reaction between rhenium metal and Cl 2 was observed below 500 C. Chlorination of technetium dioxide in molten salts has been studied here for the first time. TcO 2 reacts with HCl producing [TcCl 6 ] 2À . However, the reaction of TcO 2 with chlorine results in the oxidation of technetium to pertechnetate which is retained in the melt and production of a volatile solid, which is possibly a mixture of Tc(IV) chloride and Tc(VII) oxychloride. This is the first reported investigation into Tc speciation in molten salts.

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Spectroscopic characterization of the octachlorodirhenate(3-) ion, [Re2Cl8]3-

Cited by 11 publications

References 0 publications

Electronic Structure of Anilinopyridinate-Supported Ru₂⁵⁺ Paddlewheel Compounds

Electronic Structure of Anilinopyridinate-Supported Ru₂⁵⁺ Paddlewheel Compounds

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

Reactions and speciation of technetium and rhenium in chloride melts: a spectroscopy study

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Spectroscopic characterization of the octachlorodirhenate(3-) ion, [Re2Cl8]3-

Cited by 11 publications

References 0 publications

Electronic Structure of Anilinopyridinate-Supported Ru25+ Paddlewheel Compounds

Electronic Structure of Anilinopyridinate-Supported Ru25+ Paddlewheel Compounds

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

Reactions and speciation of technetium and rhenium in chloride melts: a spectroscopy study

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Electronic Structure of Anilinopyridinate-Supported Ru₂⁵⁺ Paddlewheel Compounds

Electronic Structure of Anilinopyridinate-Supported Ru₂⁵⁺ Paddlewheel Compounds