Vanadium complexes with hydrazone or thiosemicarbazone ligands as potential anti-mycobacterium tuberculosis agents

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Novel Scorpionate and Pyrazole Dioxovanadium Complexes, Catalysts for Carboxylation and Peroxidative Oxidation of Alkanes

The dioxovanadium(V) complexes [VO2(3,5-Me(2)Hpz)(3)][BF4] (1) (pz = pyrazolyl), [VO2{SO3C(pz)(3)}] (2), [VO2{HB(3,5-Me(2)pz)(3)}] (3) and [VO2{HC(pz)(3)}][BF4] (4), bearing pyrazole or scorpionate ligands, were obtained by reaction of triethyl vanadate [VO(OEt)(3)] with hydrotris(3,5-dimethyl-1-pyrazolyl)methane [HC(3,5-Me(2)pz)(3)] or 3,5-dimethylpyrazole (3,5-Me(2)Hpz; 1), lithium tris(1-pyrazolyl)methanesulfonate {Li[SO3C(pz)(3)], 2}, potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate {K[HB(3,5-Me(2)pz)(3)], 3} and hydrotris(1-pyrazolyl)methane [HC(pz)(3), 4], respectively. Treatment of [VO(OEt)(3)] with potassium hydrotris(1-pyrazolyl)borate {K[HB(pz)(3)]} led to the mixed eta(3)-tris(pyrazolyl)borate and eta(2)-bis(pyrazolyl)borate oxovanadium(IV) complex [VO{HB(pz)(3)}{H2B(pz)(2)}, 5]. The compounds were characterized by elemental analyses, IR, NMR and EPR spectroscopy, FAB and ESI mass spectrometry, cyclic voltammetry and, for 5, also by single crystal X-ray diffraction analysis. All complexes exhibit catalytic activity in the single-pot carboxylation [in trifluoroacetic acid/potassium peroxodisulfate (CF3COOH/K2S2O8)] of gaseous alkanes (methane and ethane) to carboxylic acids (yields up to 40%. TONs up to 157) and in the peroxidative oxidation [in water/acetonitrile (H2O/NCMe)] of liquid alkanes (cyclohexane and cyclopentane) to the corresponding alcohols and ketones (yields up to 24%, TONs up to 117), under mild conditions.

Syntheses and characterization of monomeric Mo(VI) complexes with bidentate phosphine oxide ligands and dimeric and tetrameric Mo(V) clusters with benzoic acid and phosphinic acid derivatives, containing MoO2, Mo2O2(μ-O)2 and Mo4O4(μ3-O)4

Mo(VI) oxo complexes have been persistently sought after as epoxidation catalysts. Further, Mo(V) oxo clusters of the form M4(µ3-X)4 (M = transition metal, X = O, S) have been rigorously studied due to their remarkable structures and also their usefulness as models for electronic studies. The syntheses and characterizations of new Mo(VI) and Mo(V) oxo complexes have been described in this dissertation. Two new complexes MoO2Cl2Ph2P(O)CH2COOH and MoO2Cl2Ph2P(O)C6H4tBuS(O) were synthesized from reactions of “MoO2Cl2” with ligands Ph2P(O)CH2COOH and Ph2P(O)C6H4tBuS(O). Tetrameric packing arrangements comprised of hydrogen bonds were obtained for the complex MoO2Cl2Ph2P(O)CH2COOH and the ligand Ph2P(O)CH2COOH. Further the stability of an Mo-O bond was preferred over the Mo-S bond even though this resulted in the formation of a more strained seven membered ring. Tetranuclear Mo(V) complexes of the form [Mo4(µ3-O)4(µ-O2PR2)4O4], (PR2 = PPh2, PMe2) were synthesized using reactions of MoO2(acac)2 with diphenyl and dimethyl phosphinic acids, in ethanol. In the crystal structure of these complexes four Mo=O units are interconnected by four triply bridging oxygen atoms and bridging phosphinate ligands. The complex exhibited fourfold symmetry as evidenced by a single 31P NMR peak for the P atoms in the coordinated ligands. Reaction of WO2(acac)2 with Ph2POOH in methanol resulted in a dimeric W(VI) complex [(CH3O)2(O)W(µ-O)( µ-O2PPh2)2W(O)(CH3O)2] which contained a packing disorder in its crystal structure. Similar reactions of MoO2(acac)2 with benzoic acid derivatives resulted in dimeric complexes of the form [Mo2O2(acac)2(µ-O)(µ-OC2H5)(µ-O2CR)] (R = C6H5, (o-OH)C6H4, (p-Cl)C6H4, (2,4-(OH)2)C6H3, (o-I)C6H4) and one tetrameric complex [Mo2O2(acac)2(µ-O)(µ-OC2H5)(µ-O2C)C6H4(p-µ-O2C)Mo2O2(acac)2(µ-O)(µ-OC2H5)] with terephthalic acid. 1H NMR proved very useful in the prediction of the formation of dimers with the substituted benzoic acids, which were also confirmed by elemental analyses. The reductive capability of ethanol proved instrumental in the syntheses of Mo(V) tetrameric and dimeric clusters. Synthetic details, IR, 1H and 31P NMR spectroscopy and elemental analyses are reported for all new complexes. Further, single crystal X-ray structures of MoO2Cl2Ph2P(O)CH2COOH, MoO2Cl2Ph2P(O)C6H4tBuS(O), [Mo4(µ3-O)4(µ-O2PR2)4O4], (PR2 = PPh2, PMe2), [(CH3O)2(O)W(µ-O)( µ-O2PPh2)2W(O)(CH3O)2] and [Mo2O2(acac)2(µ-O)(µ-OC2H5)(µ-O2CR)] (R = C6H5, (o-OH)C6H4) are also presented.

Spectrophotometric determination of catecholamine using vanadium and eriochrome cyanine r

A highly sensitive spectrophotometric method for the analysis of catecholamine drugs; L-dopa and methyldopa, is described. The analysis is based on the reaction of drug molecules with vanadium (V) which is reduced to vanadium (IV) and form complex with eriochrome cyanine R to give products having maximum absorbance (lmax) at 565 nm. Beer's law is obeyed in the range 0.028-0.84 and 0.099-0.996 mg mL-1 for L-dopa and methyldopa, respectively. The statistical analysis as well as comparison with reported methods demonstrated high precision and accuracy of the proposed method. The method was successfully applied in the analysis of pharmaceutical preparations.

A novel indicator reaction for the catalytic determination of V(V) at ppb levels by the kinetic spectrophotometric method

A novel sensitive and relatively selective kinetic method is presented for the determination of V(V), based on its catalytic effect on the oxidation reaction of Ponceau Xylydine by potassium bromate in presence of 5-sulfosalicylic acid (SSA) as activator. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of Ponceau Xylydine at 640 nm between 0.5 to 7 min (the fixed time method) in H3PO4 medium at 25ºC. The effect of various parameters such as concentrations of H3PO4, SSA, bromate and Ponceau Xylydine, temperature and ionic strength on the rate of net reaction were studied. The method is free from most interferences, especially from large amounts of V(IV). The decrease in absorbance is proportional to the concentration of V(V) over the entire concentration range tested (1-15 ng mL−1) with a detection limit of 0.46 ng mL-1 (according to statistical 3Sblank/k criterion) and a coefficient of variation (CV) of 1.8% (for ten replicate measurement at 95% confidence level). The proposed method suffers few interferences such as Cr(VI) and Hg(II) ions. The method was successfully applied to the determination of V(V) in tap water, drinking water, bottled mineral water samples and a certified standard reference material such as SRM-1640 with satisfactory results. The vanadium contents of water samples were also determined by FAAS for a comparison. The recovery of spiked vanadium(V) was found to be quantitative and the reproducibility was satisfactory. It was observed that the results of the SRM 1640 were in good agreement with the certified value.

INVESTIGATIONS ON THE RECOVERY OF TITANIUM VANADIUM AND IRON VALUES FROM THE WASTE CHILORIDE LIQUORS OF TITANIA INDUSTRY

The thesis entitled INVESTIDGATIONS ON THE RECOVERY OF TITANIUM VANADIUM AND IRON VALUES FROM THE WASTE CHILORIDE LIQUORS OF TITANIA INDUSTRY embodies the results of the investigations carried out on the solvent extraction separation of iron (III) vanadium(V) and titanium (IV) chlorides from the waste chloride liquors of titanium minerals processing industry by employing tributylphosphate (TBT) as an extractant. The objective of this study is to generate the knowledge base to achieve the recovery of iron, vanadium and titanium cvalues from multi- metal waste chloride liquors originating from ilmenite mineral beneficiation industries through selective separation and value added material development

Studies on metal complexes with acylhydrazones based on heterocyclic carbonyl compounds

Dept.of Applied Chemistry, Cochin University of Science and Technology

Studies on metal complexes of some tridentate acylhydrazones

Studies on transition metal complexes have achieved a great interest due to their versatile applications.The convenient route for synthesis,the nature of ligands and stability of metal complexes has significant contributions in their applications in medicine,biology,catalysis and photonics.The present work deals wth the synthesis and characterization of metal complexes of some tridentate acylhydrazones .Hydrazones are promising ligands in coordination chemistry with interesting binding modes and applications.The acylhydrazones chosen for the current study are capable of forming complexes in different forms through tautomerism.

Dithiocarbazate complexes with the [M(PPh(3))](2+) (M=Pd or Pt) moiety Synthesis, characterization and anti-Tripanosoma cruzi activity

New neutral Pd(II) and Pt(II) complexes of the type [M(L)(PPh(3))] (M Pd or Pt) were prepared in crystalline form in high-yield synthesis with the S-benzyldithiocarbazates and S-4-nitrobenzyldithiocarbazates derivatives from 2-hydroxyacetophenone, H(2)L(1a) and H(2)L(1b), and benzoylacetone, H(2)L(2a) and H(2)L(2b). The new complexes [Pt(L(1a))(PPh(3))] (1), [Pd(L(1a))(PPh(3))] (2), [Pt(L(1b))(PPh(3))] (3), [Pd(L(1b))(PPh(3))] (4), [Pt(L(2a))(PPh(3))] (5), [Pd(L(2a))(PPh(3))] (6), [Pt(L(2b))(PPh(3))] (7) and [Pd(L(2b))(PPh(3))] (8) were characterized on the basis of elemental analysis, conductivity measurements, UV-visible, IR, electrospray ionization mass spectrometry (ESI-MS), NMR ((1)H and (31)P) and by X-ray diffraction studies. The studies showed that differently from what was observed for the H(2)L(1a) and H(2)L(1b) ligands, H(2)L(2a) and H(2)L(2b) assume cyclic forms as 5-hydroxypyrazolinic. Upon coordination, H2L2a and H2L2b suffer ring-opening reaction, coordinating in the same manner as H(2)L(1a) and H(2)L(1b), deprotonated and in O,N,S-tridentate mode to the (MPPh(3))(2+) moiety. All complexes show a quite similar planar fourfold environment around the M(II) center. Furthermore, these complexes exhibited biological activity on extra and intracellular forms of Trypanosoma cruzi in a time- and concentration-dependent manner with IC(50) values ranging from 7.8 to 18.7 mu M, while the ligand H(2)L(2a) presented a trypanocidal activity on trypomastigote form better than the standard drug benznidazole. (C) 2010 Elsevier Inc. All rights reserved.

Mixed-Ligand Complexes of Technetium and Rhenium with Tridentate Benzamidines and Bidentate Benzoylthioureas

Mixed-ligand complexes of technetium(V) or rhenium(V) containing tridentate N-[(dialkylamino)(thiocarbonyl)]benzamidine (H(2)L(1)) and bidentate N,N-dialkyl-N`-benzoylthiourea (HL(2)) ligands were formed in high yields when (NBu(4))[MOCl(4)] (M = Tc or Re) or [ReOCl(3)(PPh(3))(2)] was treated with mixtures of the proligands. Other approaches for the synthesis of the products are reactions of [MOCl(L(1))] complexes with HL(2) or compounds of the-composition [ReOCl(2)(PPh(3))(L(2))] with H(2)L(1). The resulting air-stable [MO(L(1))(L(2))] complexes possess potential for the development of metal-based radiopharmaceuticals. [TcO(L(1))(L(2))] complexes are readily reduced by PPh3 with formation of [Tc(L(1))(L(2))(PPh(3))]. The resulting Tc(III) complexes undergo two almost-reversible oxidation steps corresponding to one-electron transfer processes. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Strain and vacancy cluster behavior of vanadium and tungsten-doped Ba[Zr(0.10)Ti(0.90)]O(3) ceramics

Strain and vacancy clusters behavior of polycrystalline vanadium (V) and tungsten (W)-doped Ba[Zr(0.10)Ti(0.90)]O(3), (BZT:2%V) and (BZT:2%W) ceramics obtained by the mixed oxide method was evaluated. Substitution of V and W reduces the distortion of octahedral clusters, decreasing the Raman modes. Electron paramagnetic resonance data indicate that the addition of dopants leads to defects and symmetry changes in the BZT lattice. Remnant polarization and coercive field are affected by V and W substitution due the electron-relaxation mode. The unipolar strain E curves as a function of electric field reach its maximum value for BZT:2%V and BZT:2%W ceramics. (c) 2008 American Institute of Physics.

Evaluation of Decomposition Procedure to Determine Ba, Co, Cr, Cu, Ni, Mn, V, and Zn Total Content in Soil Samples

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Polymerisationskatalysatoren auf Basis von Titan- und Vanadiumkomplexen mit Bisphenolato-Liganden

Die Synthese und Charakterisierung von Bisphenolato-Komplexen des Titans und Vanadiums werden beschrieben.Neben dem Methylkomplex wurde eine Reihe von Bisphenolato-Komplexen des Titan(IV) der Zusammensetzung (tbmp)(o-C6H4CH2NMe2)TiX (mit X = CH2SiMe3, CH2Ph, OTf) synthetisiert. Der Methylkomplex wurde mit B(C6F5)3 oder (tbmp)(tbmpH)Al zum Komplexkation [(tbmp)(o-C6H4CH2NMe2)Ti]+ umgesetzt und dessen Reaktivität gegenüber 1-Olefinen untersucht.Ausgehend von (tbmp)TiCl2 wurden der Dimethylkomplex (tbmp)TiMe2 und der Dibenzylkomplex (tbmp)Ti(CH2Ph)2 dargestellt und strukturell charakterisiert. Der Dibenzylkomplex liegt im Kristall als Dimer vor, verbrückt über ein Dioxan-Molekül, während der Dimethylkomplex auch im Feststoff monomer ist. Dies ist das erste Beispiel für die Koordinationszahl fünf bei Bisphenolato-Titan-Komplexen.Polymerisationsversuche mit (tbmp)TiMe2 und B(C6F5)3 weisen auf eine hohe Reaktivität und geringe Stabilität des aktivierten Komplexes hin, die zu geringen Polymer-Ausbeuten führt.Im Falle des Vanadiums konnten trotz Schwierigkeiten aufgrund der hohen Redoxaktivität dieses Elements mehrere Komplexe dargestellt werden. Synthetisiert und strukturell charakterisiert wurden der Komplex (mbmp)V(O)(CH2SiMe3)·B(C6F5)3, das erste Beispiel für ein Boranaddukt eines Oxokomplexes des fünfwertigen Vanadiums, und der erste Di(bisphenolato)-Komplex des vierwertigen Vanadiums, (tbmp)2V.Desweiteren gelang die Darstellung von (mbmp)V(O)(CH2SiMe2Ph)·B(C6F5)3, (tbmp)VCl(THF)2 und (mbmp)2V. Die Alkylkomplexe des fünfwertigen Vanadiums waren mit B(C6F5)3 für die Polymerisation von Ethen nicht aktivierbar. Hingegen bildete (tbmp)VCl(THF)2 mit DEAC ein sehr aktives System für die Polymerisation von Ethen.

COORDINATION CHEMISTRY OF BIS(BENZYL)PHOSPHINATE

The work presented in this dissertation deals with the coordination chemistry of the bis(benzyl)phosphinate ligand with vanadium, tungsten and cobalt. The long term goal of this project was to produce and physically characterize high oxidation state transition metal oxide phosphinate compounds with potential catalytic applications. The reaction of bis(benzyl)phosphinic acid with VO(acac)2 in the presence of water or pyridine leads to the synthesis of trimeric vanadium(IV) clusters (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(H2O) and (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(py). In contrast, when diphenylphosphinic acid or 2-hydroxyisophosphindoline-2-oxide were reacted with VO(acac)2, insoluble polymeric compounds were produced. The trimeric clusters were characterized using FTIR, elemental analysis, single crystal diffraction, room temperature magnetic susceptibility, thermogravimetric analysis and differential scanning calorimetry. The variable-temperature, solid-state magnetic susceptibility was measured on (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(py). The polymeric compounds were characterized using FTIR, powder diffraction and elemental analysis. Two different cubane clusters made of tungsten(V) and vanadium(V) were stabilized using bis(benzyl)phosphinate. The oxidation of (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(H2O) with tBuOOH led to the formation of V4(µ3-O)4(µ2-O2P(Bn)2)4(O4). W4(µ3-O)4(µ2-O2P(Bn)2)4(O4) was produced by heating W(CO)6 in a 1:1 mixture of EtOH/THF at 120 ˚C. Both compounds were characterized using single crystal diffraction, FTIR, 31P-NMR, 1H-NMR and elemental analysis. W4(µ3-O)4(µ2-O2P(Bn)2)4(O4) was also characterized using UV-vis. Cobalt(II) reacted with bis(benzyl)phosphinate to produce three different dinuclear complexes. [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4], (py)3Co(µ2-O2P(Bn)2)3Co(Cl) and (py)(µ2-NO3)Co(µ2-O2P(Bn)2)3Co(py) were all characterized using single crystal diffraction, elemental analysis and FTIR. Room temperature magnetic susceptibility measurements were performed on [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4] and (py)3Co(µ2-O2P(Bn)2)3Co(Cl). The variable-temperature, solid-state magnetic susceptibility was also measured on [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4].

Mechanical behavior of tungsten-vanadium-lanthana alloys as function of temperature

The mechanical behavior of three tungsten (W) alloys with vanadium (V) and lanthana (La2O3) additions (W–4%V, W–1%La2O3, W–4%V–1%La2O3) processed by hot isostatic pressing (HIP) have been compared with pure-W to analyze the influence of the dopants. Mechanical characterization was performed by three point bending (TPB) tests in an oxidizing air atmosphere and temperature range between 77 (immersion tests in liquid nitrogen) and 1273 K, through which the fracture toughness, flexural strength, and yield strength as function of temperature were obtained. Results show that the V and La2O3 additions improve the mechanical properties and oxidation behavior, respectively. Furthermore, a synergistic effect of both dopants results in an extraordinary increase of the flexure strength, fracture toughness and resistance to oxidation compared to pure-W, especially at higher temperatures. In addition, a new experimental method was developed to obtain a very small notch tip radius (around 5–7 μm) and much more similar to a crack through the use of a new machined notch. The fracture toughness results were lower than those obtained with traditional machining of the notch, which can be explained with electron microscopy, observations of deformation in the rear part of the notch tip. Finally, scanning electron microscopy (SEM) examination of the microstructure and fracture surfaces was used to determine and analyze the relationship between the macroscopic mechanical properties and the micromechanisms of failure involved, depending on the temperature and the dispersion of the alloy.