pH-Specific Structural Speciation of the Ternary V(V)–Peroxido–Betaine System: A Chemical Reactivity-Structure Correlation

Gabriel, Catherine; Kioseoglou, Efrosini; Venetis, J.; Psycharis, Vassilis; Raptopoulou, Catherine P.; Terzis, Aris; Voyiatzis, George A.; Bertmer, Marko; Mateescu, C.; Salifoglou, Athanasios

doi:10.1021/ic2025878

Cited by 17 publications

(3 citation statements)

References 110 publications

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“…The V-V interatomic distance in the dinuclear assembly is 3.396 Å, and the distances to peroxide-O atoms acting as bridges are [V1-O2, 1.877(3) Å and V1-O2A, 2.419(3) Å]. Such peroxido bridges are very unusual in the literature 25. Compound 6a crystallized from methanol as orange prisms and Fig.7depicts an ORTEP representation.…”

mentioning

confidence: 77%

Oxidovanadium(iv) and dioxidovanadium(v) complexes of hydrazones of 2-benzoylpyridine and their catalytic applications

et al. 2015

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Reactions between the tridentate ONN donor ligands, Hbzpy-tch () and Hbzpy-inh (), with [V(IV)O(acac)2] in dry methanol give two different types of complexes, [V(IV)O(acac)(bzpy-tch)] () and [V(IV)O(OMe)(bzpy-inh)] (), respectively. Irrespective of their nature in methanol upon aerial oxidation and precipitation both yield dinuclear [{V(V)O(bzpy-tch)}2(μ-O)2] () and [{V(V)O(bzpy-inh)}2(μ-O)2] (). Treatment of or in methanol with H2O2 yields the oxidomonoperoxidovanadium(v) complexes [{V(V)O(bzpy-tch)}2(μ-O2)2] () and [V(V)O(O2)(bzpy-inh)] (). Reactions of and with imidazolomethylpolystyrene cross-linked with 5% divinylbenzene (PS-im) in DMF give the polymer-supported PS-im[V(V)O2(bzpy-inh)] () and PS-im[V(V)O2(bzpy-tch)] (). The compounds are characterized by various spectroscopic techniques and compounds and were also analyzed by thermal, atomic force microscopy (AFM), field-emission scanning electron micrographs (FE-SEM) as well as energy dispersive X-ray (EDAX) studies. The molecular structures of and of [V(V)O(O2)(bzpy-inh)(H2O)]·0.5MeOH () were determined by single-crystal X-ray diffraction, confirming the μ-bis(O) and ONN binding mode in the dinuclear complexes and , as well as the side-on coordination of the peroxido ligand in and . The polymer-grafted compounds and were used for the catalytic oxidation of isoeugenol using aqueous H2O2 as an oxidant. The intermediate peroxido species, expected to be involved during catalytic action, were also generated from solutions of and studied by UV-Vis and (51)V NMR. The catalytic activity of the several systems was tested and the polymer-supported versions showed higher conversions than their neat counterparts. The polymer-supported complexes allow for recyclable catalytic systems, thus providing additional advantages over their homogeneous counterparts in terms of increased catalyst lifetime and easier separation from the reaction mixture.

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confidence: 77%

Oxidovanadium(iv) and dioxidovanadium(v) complexes of hydrazones of 2-benzoylpyridine and their catalytic applications

et al. 2015

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“…[42] For other closely relatedc omplexes, the pattern followed that of aN a 3 VO 4 /H 2 O 2 mixture (1:1 molar ratio), showingasudden increase in cytotoxicity at > 0.10 mm V. [42] Both results were consistent with decomposition of the originalc omplexes in cell culture media. The most detailedb iological studies were performed foraV V -peroxidobetaine complex, 3, [56,57] but its graduald ecomposition in water was only briefly mentioned, [58] and no kinetic data were given. High cytotoxicity (IC 50 < 1.0 mm at 96 h) was observed for [V V O(O 2 ) 2 (phen)] À (where phen = 1,10-phenanthroline or 4,7-dimethyl-1,10-phenanthroline) in aw idev ariety of cancer cell lines, [38] butitw as mostlikely due to the release of phen ligands (Section 2.5).…”

Section: Peroxido V V Complexesmentioning

confidence: 99%

Stabilities and Biological Activities of Vanadium Drugs: What is the Nature of the Active Species?

Levina

Lay

2017

Chemistry An Asian Journal

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Diverse biological activities of vanadium(V) drugs mainly arise from their abilities to inhibit phosphatase enzymes and to alter cell signaling. Initial interest focused on anti-diabetic activities but has shifted to anti-cancer and anti-parasitic drugs. V-based anti-diabetics are pro-drugs that release active components (e.g., H VO ) in biological media. By contrast, V anti-cancer drugs are generally assumed to enter cells intact; however, speciation studies indicate that nearly all drugs are likely to react in cell culture media during in vitro assays and the same would apply in vivo. The biological activities are due to V and/or V reaction products with cell culture media, or the release of ligands (e.g., aromatic diimines, 8-hydroxyquinolines or thiosemicarbazones) that bind to essential metal ions in the media. Careful consideration of the stability and speciation of V complexes in cell culture media and in biological fluids is essential to design targeted V-based anti-cancer therapies.

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“…[38][39][40][41][42][43][44][45][46] Hence, Pb-based CPs find potential applications as luminescent materials, [47][48][49][50][51][52] ion exchangers 53 and nonlinear optical materials. 54 As PbĲII) cations have an affinity towards organic ligands containing O, N and S donor atoms, [55][56][57][58][59] hydrazone containing building blocks are often employed in the construction of PbĲII) coordination compounds, also due to their excellent coordinating ability, versatile coordination modes, and possible supramolecular interactions.…”

Section: Introductionmentioning

confidence: 99%

Metal–organic and supramolecular lead(ii) networks assembled from isomeric nicotinoylhydrazone blocks: the effects of ligand geometry and counter-ion on topology and supramolecular assembly

et al. 2016

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A new series of six structurally diverse leadĲII) coordination compounds was assembled from two isomeric nicotinoylhydrazones as neutral ligands and three PbĲII) salts with different monoanions (chloride, nitrate and thiocyanate) as starting materials. The products were isolated in good yields and were fully characterized, including by single-crystal X-ray diffraction and theoretical methods. Within the six compounds, three feature 2D metal-organic networks, two are 1D coordination polymers, and another one comprises discrete 0D dimeric units. The structures of the latter low dimensional compounds are extendable into 2D supramolecular networks. The topology of the coordination or supramolecular networks is primarily dictated by the geometry of the nicotinoylhydrazone used as a main building block. In contrast, supramolecular interactions are greatly influenced by the choice of the anion in the starting leadĲII) salt, which is demonstrated by Hirshfeld surface analysis. In fact, the topological analysis and classification of metal-organic or supramolecular underlying networks in the obtained compounds was performed, disclosed the hcb, 2C1, gek1, SP 1-periodic net (4,4)(0,2) and 3,4L83 topological types; the latter topology was documented for three compounds, including both coordination and supramolecular networks. In the two compounds containing thiocyanate moieties, there are supramolecular contacts between the thiocyanate anions and lead centres. These were shown by DFT calculations to be strong tetrel bonds (−15.3 and −16.7 kcal mol −1 ) between the σ-hole of the lead atom and the π-system of the thiocyanate S-C bond.CrystEngComm, 2016, 18, 5375-5385 | 5375This journal is

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pH-Specific Structural Speciation of the Ternary V(V)–Peroxido–Betaine System: A Chemical Reactivity-Structure Correlation

Cited by 17 publications

References 110 publications

Oxidovanadium(iv) and dioxidovanadium(v) complexes of hydrazones of 2-benzoylpyridine and their catalytic applications

Oxidovanadium(iv) and dioxidovanadium(v) complexes of hydrazones of 2-benzoylpyridine and their catalytic applications

Stabilities and Biological Activities of Vanadium Drugs: What is the Nature of the Active Species?

Metal–organic and supramolecular lead(ii) networks assembled from isomeric nicotinoylhydrazone blocks: the effects of ligand geometry and counter-ion on topology and supramolecular assembly

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