Hexazirconium‐ and Hexahafnium‐Containing Tungstoarsenates(III) and Their Oxidation Catalysis Properties

Al-Kadamany, Ghada; Mal, Sib Sankar; Milev, Borislav P.; Donoeva, Baira; Maksimovskaya, R. I.; Kholdeeva, Oxana A.; Kortz, Ulrich

doi:10.1002/chem.201000786

Cited by 61 publications

(28 citation statements)

References 29 publications

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“…The Zr–O bond lengths vary from 2.055(7) to 2.386(7) Å (Table S2). On the basis of the structural description of 1 , the central Zr 4 cluster is linked into a zonal pattern and the four Zr atoms present a diamondoid‐like mode similar to that reported previously in which the central Zr–O cluster was decorated by a water molecule, acetate,, , [4a] mandelate[3a] or Tris(hydroxymethyl)‐methyl aminomethane. [4b]…”

Section: Resultsmentioning

confidence: 99%

An Oxalate‐Functionalized Tetra‐Zr^IV‐Substituted Sandwich‐Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers

Wang

Zhang

et al. 2018

Eur J Inorg Chem

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A previously unknown inorganic-organic hybrid polyoxidometalate constructed from oxalate-functionalized tetra-Zr IV -substituted dimeric silicotungstate, (NH 4 ) 3 Na 5 K 6 -[Zr 4 (μ 3 -O) 2 (μ-OH) 2 (ox) 2 (SiW 10 O 37 ) 2 ]·23H 2 O (1, ox = oxalate) has been synthesized under mild hydrothermal conditions and characterized by FTIR spectroscopy, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction.[a]

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Section: Resultsmentioning

confidence: 99%

An Oxalate‐Functionalized Tetra‐Zr^IV‐Substituted Sandwich‐Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers

Wang

Zhang

et al. 2018

Eur J Inorg Chem

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“…31 P NMR spectroscopy is a powerful tool to study the possible equilibria of different Zr IV ‐substituted WD POMs present in solution . The two phosphorus atoms in the WD structures are not chemically identical, thus resulting in two distinct singlets in a 31 P NMR spectrum.…”

Section: Resultsmentioning

confidence: 99%

Interaction Study and Reactivity of Zr^IV‐Substituted Wells–Dawson Polyoxometalate towards Hydrolysis of Peptide Bonds in Surfactant Solutions

Quanten

Shestakova

Bulck

et al. 2016

Chemistry A European J

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The interaction between the 1:2 Zr(IV) :Wells-Dawson complex, K15 H[Zr(α2 -P2 W17 O61 )2] (1), and a range of surfactants was studied in detail with the aim of developing metal-substituted POMs as potential artificial proteases for membrane proteins. The surfactants include the positively charged cetyl(trimethyl)ammonium bromide (CTAB), the negatively charged sodium dodecyl sulfate (SDS), the neutral Triton X-100 (TX-100), and zwitterionic 3-[dodecyl(dimethyl)ammonio]-1-propanesulfonate (Zw3-13) and 3-[dimethyl(3-{[(3α,5β,7α,12α)-3,7,12-trihydroxy-24-oxocholan-24-yl]amino}propyl)ammonio]-1-propanesulfonate (CHAPS). A combination of multinuclear (1)H, (13)C, and (31) P NMR spectroscopy, (1)H diffusion-ordered NMR spectroscopy ((1)H DOSY), and nuclear Overhauser effect spectroscopy (NOESY) was used to examine the interaction between 1 and each surfactant on the molecular level. Cationic surfactant CTAB caused precipitation of 1 due to strong electrostatic interactions, while the anionic SDS and neutral TX-100 surfactants did not exhibit any interaction at neutral pD. (1)H DOSY NMR spectroscopy indicated an interaction between 1 and zwitterionic surfactants Zw3-12 and CHAPS, which occurs via the positively charged ammonium group in the surfactant molecule. In the presence of anionic, neutral, and zwitterionic surfactants, 1 preserves its catalytic activity towards the hydrolysis of the peptide bond in the dipeptide glycyl-l-histidine (GH). The fastest hydrolysis was observed at pD 7.0 and could be rationalized by taking into account pD-dependent speciation of 1 and coordination properties of GH.

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“…These species are generally obtained by complexation of the tetravalent cations (sometimes mixed with 3d metals) by vacant Keggin‐ or Dawson‐type polyoxotungstates, giving rise to 1:2 sandwich‐type compounds such as [M IV (XW 11 O 39 ) 2 ] 12– or [M IV (XW 17 O 61 ) 2 ] 16– (with M = U, Th, Np, Pu, Cm and X = As, P, Si, Ge) or more complex systems with polyvacant units . Some rare examples of POMs stabilizing trimeric or hexameric condensed zirconium or hafnium cations were also synthesized by other research groups , . From a synthetic point of view, these polynuclear tetravalent compounds are relatively difficult to isolate as they tend to form oligomers that precipitate in solution and are usually obtained by combination of organic and inorganic chelating agents .…”

Section: Introductionmentioning

confidence: 99%

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core

et al. 2016

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The reaction of Na10[α‐SiW9O34] with 4f tetravalent cerium cations in aqueous solution in the presence of sodium acetate at different pH values leads to the stabilization of three cerium‐based polyanionic molecular clusters [Ce3(µ2‐OH)3(µ3‐O)(SiW9O34)2]13– (1), [Ce3(µ2‐O)3(SiW9O34)2]14– (2), and {[Ce6(µ3‐O)4(µ3‐OH)4]2(W8O32)(SiW9O34)4}32– (3). The condensation behavior of cerium in this kind of association with trivacant polyoxometalates (POMs) when a pH variation occurs is relatively unknown and needed to be explored. Compounds 1 and 2 consist of a trinuclear cerium cluster fragment stabilized by two POM moieties with a variation of the central cerium cluster from [Ce3(µ2‐OH)3(µ3‐O)] to [Ce3(µ2‐O)3]. Compound 3 appears much more condensed with two hexanuclear [Ce6(µ3‐O)4(µ3‐OH)4] groups that are stabilized by the SiW9O34 moieties and a W8O32 tungsten ring. This evolution in cluster size and composition reflects the pH variation applied during their synthesis. The molecules have been characterized by single‐crystal X‐ray diffraction, 183W and 29Si NMR spectroscopy, IR spectroscopy, thermogravimetric analysis (TGA), and SEM/energy‐dispersive X‐ray (EDX) microscopy. The three compounds obtained here exemplify the influence of pH on the condensation of tetravalent cations and open a new route toward the stabilization of polynuclear tetravalent clusters by nucleophilic O‐donating POM species.

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Hexazirconium‐ and Hexahafnium‐Containing Tungstoarsenates(III) and Their Oxidation Catalysis Properties

Cited by 61 publications

References 29 publications

An Oxalate‐Functionalized Tetra‐Zr^IV‐Substituted Sandwich‐Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers

An Oxalate‐Functionalized Tetra‐Zr^IV‐Substituted Sandwich‐Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers

Interaction Study and Reactivity of Zr^IV‐Substituted Wells–Dawson Polyoxometalate towards Hydrolysis of Peptide Bonds in Surfactant Solutions

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core

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Hexazirconium‐ and Hexahafnium‐Containing Tungstoarsenates(III) and Their Oxidation Catalysis Properties

Cited by 61 publications

References 29 publications

An Oxalate‐Functionalized Tetra‐ZrIV‐Substituted Sandwich‐Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers

An Oxalate‐Functionalized Tetra‐ZrIV‐Substituted Sandwich‐Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers

Interaction Study and Reactivity of ZrIV‐Substituted Wells–Dawson Polyoxometalate towards Hydrolysis of Peptide Bonds in Surfactant Solutions

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW9O34]10– Leading to the Formation of a Ce6O4(OH)4 Core

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An Oxalate‐Functionalized Tetra‐Zr^IV‐Substituted Sandwich‐Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers

An Oxalate‐Functionalized Tetra‐Zr^IV‐Substituted Sandwich‐Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers

Interaction Study and Reactivity of Zr^IV‐Substituted Wells–Dawson Polyoxometalate towards Hydrolysis of Peptide Bonds in Surfactant Solutions

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core