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Polyoxometalate

About: Polyoxometalate is a research topic. Over the lifetime, 3493 publications have been published within this topic receiving 94123 citations. The topic is also known as: POM.


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Journal ArticleDOI
TL;DR: The crystal structure shows that the monomeric form is stabilized by electrostatic and water-mediated hydrogen bonding interactions with the protein, demonstrating high selectivity towards peptide bonds containing this residue.
Abstract: The effect of the protein environment on the formation and stabilization of an elusive catalytically active polyoxometalate (POM) species, K6 [Hf(α2 -P2 W17 O61 )] (1), is reported. In the co-crystal of hen egg-white lysozyme (HEWL) with 1, the catalytically active monomeric species is observed, originating from the dimeric 1:2 POM form, while it is intrinsically unstable under physiological pH conditions. The protein-assisted dissociation of the dimeric POM was rationalized by means of DFT calculations. The dissociation process is unfavorable in bulk water, but becomes favorable in the protein-POM complex due to the low dielectric response at the protein surface. The crystal structure shows that the monomeric form is stabilized by electrostatic and water-mediated hydrogen bonding interactions with the protein. It interacts at three distinct sites, close to the aspartate-containing hydrolysis sites, demonstrating high selectivity towards peptide bonds containing this residue.

41 citations

Journal ArticleDOI
TL;DR: In this paper, the isolation and structural characterisation of a tris[peroxotitanium(IV)]-substituted α-Dawson polyoxometalate (POM), [α-1,2,3-P2W15(TiO2)3O56(OH)3]9− (1a), containing side-on coordination (i.e. η2-coordination) of the peroxo group to the titanium(IV) atom are described.
Abstract: The isolation and structural characterisation of a novel tris[peroxotitanium(IV)]-substituted α-Dawson polyoxometalate (POM), [α-1,2,3-P2W15(TiO2)3O56(OH)3]9− (1a), containing side-on coordination (i.e. η2-coordination) of the peroxo group to the titanium(IV) atom are described. A water-soluble, completely inorganic compound of the monomeric POM Na9[α-1,2,3-P2W15(TiO2)3O56(OH)3]·16H2O (1), obtained as analytically pure, homogeneous orange crystals, was obtained from a reaction in aqueous solution of an excess of 30% aqueous hydrogen peroxide with {[α-1,2,3-P2W15Ti3O59(OH)3]4[μ3-Ti(OH)3]4Cl}33− (2a). The latter has been recently shown to be a giant ”tetrapod”-shaped, tetrameric anhydride formed from the tris[titanium(IV)]-substituted Dawson substructures with four bridging Ti octahedral groups. Compound 1 could not be obtained from the reaction with another giant tetrapod POM, {[α-1,2,3-P2W15Ti3O57.5(OH)3]4Cl}25− (3a), which does not contain the bridging octahedral Ti groups. The molecular structure of 1a was successfully determined by a single-crystal X-ray diffraction study and was shown to be a monomeric α-Dawson POM derived from the tris[peroxotitanium(IV)] species. Bond valence sum (BVS) calculations suggest that the μ2-oxo sites of the three Ti−O−Ti bridges in the Ti3 cap of the Dawson unit are protonated. Characterisation of 1 was also accomplished by complete elemental analysis, TG/DTA, FTIR and solution (31P and 183W) NMR spectroscopy. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

41 citations

Journal ArticleDOI
TL;DR: In this paper, the hexamolybdate framework serves as an octahedral nexus for six terminal arylimido ligands, and the 2,6-diisopropylphenyl isocyanate (ArNCO) affords the title of the most abundant ligand.

41 citations

Journal ArticleDOI
TL;DR: Comprehensive theoretical, analytical, and catalytic studies identify the active role of the Sb atom in the polyoxometalate metal belt and sheds new light on low-cost catalyst tuning strategies for crucial oxidative transformations.
Abstract: Catalytic belts are the crucial feature of Zn/Sb-polyoxometalates as efficient and selective catalysts for alcohol oxidation. Comprehensive theoretical, analytical, and catalytic studies identify the active role of the Sb atom in the polyoxometalate metal belt. This sheds new light on low-cost catalyst tuning strategies for crucial oxidative transformations.

41 citations

Journal ArticleDOI
TL;DR: The novel 8-coordinate zirconium compound (NH(4))(6)[Zr(PMo(12)O(40)](3)(-), and monovacant lacunary, [PMo (11)O (39)](7)(-) anion has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, and vibrational and (31)P NMR spectroscopy.
Abstract: The novel 8-coordinate zirconium compound (NH4)6[Zr(PMo12O40)(PMo11O39)]·26H2O (1) has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, and vibrational and 31P NMR spectroscopy. It is the first example of a metal complex containing both parent, [PMo12O40]3-, and monovacant lacunary, [PMo11O39]7-, anions. Furthermore, this is the first crystallographic determination of the [PMo11O39]7- anion.

41 citations


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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
2023246
2022566
2021213
2020218
2019187
2018216