Protonolysis of [(iPrO)TiMo5O18]3−: access to a family of TiMo5Lindqvist type polyoxometalates

Three inorganic-organic-inorganic hybrids of dipalladium-substituted γ-Keggin silicodecatungstates with organic linkers of different lengths, TBA8[{(γ-H2SiW10O36Pd2)(O2C(CH2)nCO2)}2] (n = 1 (II), 3 (III), and 5 (IV), TBA = [(n-C4H9)4N](+)), were synthesized by exchange of the acetate ligands in TBA4[γ-H2SiW10O36Pd2(OAc)2] (ITBA) with malonic, glutaric, and pimelic acids, respectively. The X-ray crystallographic analysis of II, IIIA (IIIA: III with DCE, DCE = 1,2-dichloroethane), and IVA (IVA: IV with 10DCE) revealed that the anion parts of II, IIIA, and IVA were inorganic-organic-inorganic hybrids composed of two dipalladium-substituted γ-Keggin silicodecatungstates connected by two dicarboxylate ligands. In the crystal structure of IVA, 10 DCE molecules per polyanion were present in the vicinity of polyanions. Compound IVB (IVB: IV with 0.2DCE) was obtained by the evacuation of IVA. The DCE sorption-desorption isotherms of IVB showed that the amount of DCE sorbed was saturated at 10.5 mol mol(-1), of which the amount was close to that (10 mol mol(-1)) of crystallographically assigned DCE molecules. In the DCE sorption-desorption isotherms, a low-pressure hysteresis was observed probably because of hydrogen-bonding interaction between DCE molecules and polyanions. The powder X-ray diffraction (XRD) pattern of IVA changed with decrease in the relative DCE vapor pressure to form IVC (IVC: IV with 0.7DCE) at P/P0 = 0.0. The in situ powder XRD study showed reversible structure transformation between IVA and IVC driven by the sorption-desorption of DCE.

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“…The synthesis of POM-based hybrids by the use of ligand exchange of acetate ligands in TMSPs has never been reported. , …”

Section: Resultsmentioning

confidence: 96%

Synthesis and Structural Characterization of Inorganic-Organic-Inorganic Hybrids of Dipalladium-Substituted γ-Keggin Silicodecatungstates

et al. 2013

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“…Coyle et al reported a series of polyoxomolybdates formed from protonolysis of [(iPrO)TiMo 5 O 18 ] 3À [116]. 17 O NMR was used to characterise the molecules in solution and revealed the relative basicities of the complexes, which was attributed to the electron donating ability of the heteroatomligand unit.…”

Section: Solution Dynamics Of Nanometer-sized Aqueous Cluster Ionsmentioning

confidence: 99%

17 O NMR as a Tool in Discrete Metal Oxide Cluster Chemistry

Ohlin

Casey

2018

Annual Reports on NMR Spectroscopy

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This chapter covers recent developments in 17 O NMR spectroscopy as applied to discrete metal oxide clusters, particularly in the context of their use as models in geochemistry and catalysis. Dynamic 17 O NMR methods based on the McConnell-Bloch equations are explored in depth, and recent advances are reviewed. High-pressure NMR methods are also discussed and reviewed, as are recent developments in the use of density functional theory in the computation of 17 O NMR shifts in polyoxometalates. The emphasis of the chapter is on the new developments that promise to reinvigorate 17 O NMR as a central tool in the study of aqueous chemical kinetics, with the most urgent challenges being understanding the rates of isotopic substitution into bridging oxygens in clusters.

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“…Mixed-metal alkoxides are often seen as suitable precursors, undergoing thermal decomposition to oxides under extremely mild conditions, most often in the range 150−180 °C. 13 Even the reports on bimetal titanium−molybdenum alkoxide derivatives appeared very scarce in the literature, with only two compounds, ( n Bu 4 N) 3 [( i PrO)TiMo 5 O 18 ] 14,15 and [{Ti 4 Mo V 2 O 8 (OEt) 10 } 2 ], 16 having compositions not corresponding to that of the target oxide phase. We saw therefore as our aim to develop synthetic approaches and produce structural characterization for bimetallic titanium−molybdenum alkoxides with a 1:1 composition, utilize them in the synthesis of a TiMoO 5 material, and finally, investigate its structure and electrochemical properties to verify its potential applicability as an anode material for Li ion batteries.…”

Section: ■ Introductionmentioning

confidence: 99%

Single-Source Alkoxide Precursor Approach to Titanium Molybdate, TiMoO₅, and Its Structure, Electrochemical Properties, and Potential as an Anode Material for Alkali Metal Ion Batteries

et al. 2021

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Transition-metal oxide nanostructured materials are potentially attractive alternatives as anodes for Li ion batteries and as photocatalysts. Combining the structural and thermal stability of titanium oxides with the relatively high oxidation potential and charge capacity of molybdenum(VI) oxides was the motivation for a search for approaches to mixed oxides of these two metals. Challenges in traditional synthetic methods for such materials made development of a soft chemistry single-source precursor pathway our priority. A series of bimetallic Ti-Mo alkoxides were produced by reactions of homometallic species in a 1:1 ratio. Thermal solution reduction with subsequent reoxidation by dry air offered in minor yields Ti 2 Mo 2 O 4 (OMe) 6 (O i Pr) 6 ( 1 ) by the interaction of Ti(O i Pr) 4 with MoO(OMe) 4 and Ti 6 Mo 6 O 22 (O i Pr) 16 (iPrOH) 2 ( 2 ) by the reaction of Ti(O i Pr) 4 with MoO(O i Pr) 4 . An attempt to improve the yield of 2 by microhydrolysis, using the addition of stoichiometric amounts of water, resulted in the formation with high yield of a different complex, Mo 7 Ti 7+ x O 31+ x (O i Pr) 8+2 x ( 3 ). Controlled thermal decomposition of 1 – 3 in air resulted in their transformation into the phase TiMoO 5 ( 4 ) with an orthorhombic structure in space group Pnma , as determined by a Rietveld refinement. The electrochemical characteristics of 4 and its chemical transformation on Li insertion were investigated, showing its potential as a promising anode material for Li ion batteries for the first time. A lower charge capacity and lower stability were observed for its application as an anode for a Na ion battery.

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Protonolysis of [(ⁱPrO)TiMo₅O₁₈]³⁻: access to a family of TiMo₅Lindqvist type polyoxometalates

Cited by 21 publications

References 40 publications

Synthesis and Structural Characterization of Inorganic-Organic-Inorganic Hybrids of Dipalladium-Substituted γ-Keggin Silicodecatungstates

Synthesis and Structural Characterization of Inorganic-Organic-Inorganic Hybrids of Dipalladium-Substituted γ-Keggin Silicodecatungstates

17 O NMR as a Tool in Discrete Metal Oxide Cluster Chemistry

Single-Source Alkoxide Precursor Approach to Titanium Molybdate, TiMoO₅, and Its Structure, Electrochemical Properties, and Potential as an Anode Material for Alkali Metal Ion Batteries

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Protonolysis of [(iPrO)TiMo5O18]3−: access to a family of TiMo5Lindqvist type polyoxometalates

Cited by 21 publications

References 40 publications

Synthesis and Structural Characterization of Inorganic-Organic-Inorganic Hybrids of Dipalladium-Substituted γ-Keggin Silicodecatungstates

Synthesis and Structural Characterization of Inorganic-Organic-Inorganic Hybrids of Dipalladium-Substituted γ-Keggin Silicodecatungstates

17 O NMR as a Tool in Discrete Metal Oxide Cluster Chemistry

Single-Source Alkoxide Precursor Approach to Titanium Molybdate, TiMoO5, and Its Structure, Electrochemical Properties, and Potential as an Anode Material for Alkali Metal Ion Batteries

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Product

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Protonolysis of [(ⁱPrO)TiMo₅O₁₈]³⁻: access to a family of TiMo₅Lindqvist type polyoxometalates

Single-Source Alkoxide Precursor Approach to Titanium Molybdate, TiMoO₅, and Its Structure, Electrochemical Properties, and Potential as an Anode Material for Alkali Metal Ion Batteries