Polyoxo alkoxides of vanadium: the structures of the decanuclear vanadium(IV) clusters [V10O16{CH3CH2C(CH2O)3}4]4- and [V10O13{CH3CH2C(CH2O)3}5]-

Khan, M. Ishaque; Chen, Qin; Goshorn, D. P.; Hope, H.; Parkin, Sean; Zubieta, Jon

doi:10.1021/ja00035a027

Cited by 92 publications

(48 citation statements)

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“…In fact, the first reported NADH-vanadate reductase by Erdmann et al [71] was later found to be specific for V 10 and the reduction to vanadyl was confirmed by EPR [73]. It has not been determined which oxovanadate species undergo reduction and the possibility that V 10 could be more prone to reduction than the metavanadates is supported by literature observations [74,75]. The ability of V 10 to undergo redox chemistry compatible with biological conditions was confirmed in studies subjecting decavanadate to photoreduction [68,69,76] and protein photocleavage was observed [77].…”

Section: Decavanadate Structure Formation Stability and Reductionmentioning

confidence: 97%

Decavanadate (V10O286-) and oxovanadates: Oxometalates with many biological activities

Aureliano

Crans

2009

Journal of Inorganic Biochemistry

227

249

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Section: Decavanadate Structure Formation Stability and Reductionmentioning

confidence: 97%

Decavanadate (V10O286-) and oxovanadates: Oxometalates with many biological activities

Aureliano

Crans

2009

Journal of Inorganic Biochemistry

227

249

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“…Reactions with polydentate O-functional ligands have demonstrated a variety of reactivities. The Zubieta group has undertaken studies with the ligand tris(hydroxymethyl)ethane, and a range of decamers and other oxometalates have been capped with this ligand and structurally characterized [108][109][110][111]. These complexes are important not only because they document the electronic properties of such derivatives, but also because they show, for example, that a decamer, which is a very stable system in aqueous systems, readily undergoes substitution reactions on the oxometalate surface in the absence of water.…”

Section: How Do Vanadium Complexes React In Organic Solvents?mentioning

confidence: 99%

Fifteen years of dancing with vanadium

Crans

2005

Pure and Applied Chemistry

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“…Of particular note are vanadate(IV) species based on the hexametalate ( Figure 2) and decavanadate ( Figure 1) cores with alkoxy oxygens in surface bridging positions. 31 Heteroatom Derivatives. Complexes in which the primary heteroatom bears an organic group form another class of heteropolyanion derivatives.…”

Section: Organic Derivatives and Functionalizationmentioning

confidence: 99%

PolyoxometalatesUpdate based on the original article by Michael T. Pope,Encyclopedia of Inorganic Chemistry© 2005, John Wiley & Sons, Ltd.

Pope¹,

Kortz²

2012

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The class of complexes known as polyoxometalates (POMs) is predominantly populated by polyoxoanions of high‐valent (d 0 , d 1 ) transition metals of groups 5 and 6 that typically incorporate some 5‐50 metal centers in structures of high symmetry. In most cases, the metal atoms occupy {MO 6 } octahedra that share vertices and edges. However, recent reports of POMs that incorporate square‐planar {Pd II O 4 } and hexagonal‐bipyramidal {U VI O 2 (η 2 − O 2 ) 2 (OH) 2 } building blocks indicate that further expansion of the field is in progress. The descriptive chemistry of many polyoxomolybdates and polyoxotungstates dates from the last third of the nineteenth century but it was not until the mid‐twentieth century that structural principles and the aqueous equilibria controlling the formation of POMs from monomeric oxoanions began to be recognized and quantified. That additional heteroatoms (metallic or nonmetallic) can be incorporated into the structures of, especially, polymolybdates and tungstates accounts for the enormous and rapidly developing variety of structures and possible applications of POMs. Four general types of POM structure, based on the mode of incorporation of the heteroatom(s), are described and it is shown how these can lead to hybrid organo‐POM complexes and to functionalization of POMs. Certain POM structures are reducible to mixed‐valence “heteropoly blue” versions, and those incorporating domains of paramagnetic heteroatoms can exhibit single‐molecule magnetic properties. The possibility that Mo VI and W VI can occupy a seven‐coordinate {O = M(O 6 )} polyhedron in POMs was first observed in [Mo 36 O 112 (H 2 O) 8 ] 8− {Mo 36 }; subsequent work has led to the development of other macrosized POMs including rings {Mo 154 }, hollow icosahedral “Keplerates” {Mo 60 W 72 }, and the “blue hedgehog” {Mo 368 }. Aqueous and aqueous‐organic solutions of such macro‐POMs spontaneously form hollow spherical vesicular structures (“blackberries”) with diameters typically 90 nm, with inter‐POM separations of 1 nm, depending upon the dielectric constant of the solvent. The various properties of POMs (such as large size, high molecular weight, solubility in polar and nonpolar solvents, electron and proton transfer and storage capacity, high thermal stability) have sparked applications in several fields, most notably in catalysis, both heterogeneous and homogeneous. Other applications include their use as electron‐dense staining and imaging agents, and their antiviral and antitumoral activity. Unconventional POMs are mainly represented by polyoxopalladates(II) and polyperoxodioxouranates(VI), which are also isolated from aqueous media. Unlike the early transition‐metal‐based POMs, the palladate structures are terminated by heteroatom groups and may also contain an internal heteroatom. The class of polyperoxodioxouranates(VI) isolated from more alkaline media frequently have fullerene‐like structures based on hexagonal bipyramidal bipyramids linked by η 2 ‐peroxo groups and hydroxo, oxalato, diphosphato, or diphosphonato bridges.

show abstract

Polyoxo alkoxides of vanadium: the structures of the decanuclear vanadium(IV) clusters [V10O16{CH3CH2C(CH2O)3}4]4- and [V10O13{CH3CH2C(CH2O)3}5]-

Cited by 92 publications

References 0 publications

Decavanadate (V10O286-) and oxovanadates: Oxometalates with many biological activities

Decavanadate (V10O286-) and oxovanadates: Oxometalates with many biological activities

Fifteen years of dancing with vanadium

PolyoxometalatesUpdate based on the original article by Michael T. Pope,Encyclopedia of Inorganic Chemistry© 2005, John Wiley & Sons, Ltd.

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