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We have synthesized a mu-oxido divanadium compound [(VOL) 2(mu-O)] with an aliphatic hydrazone ligand LH2 = (E)-N’-(1-(2-hydroxyphenyl)ethylidene)acetohydrazide. The complex was characterized by elemental analysis, IR and UV-Vis spectroscopy and the molecular structure was established by single crystal X-ray diffraction technique. The complex has been infused over alumina to prepare a heterogeneous catalyst which was characterized by IR spectroscopy, thermogravimetric and powder XRD analyses. The catalyst has been studied for the oxidation of styrene in presence of H2O2 and appears to be easily recyclable. A conversion of 99.7% and selectivity of 88.1% for benzaldehyde formation and a turnover number of 1354 was detected under the most favorable reaction conditions.

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Reference:
Metal catalyst and ligand design,
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The reaction of [VO(acac)2], methylenediphosphonic acid and triethylamine in acetonitrile at 110C for 60 h yields (Et3NH)2-[(VO)2(acac)2(O 3PCH2PO3)] (1). The structure of 1 consists of two {VO(acac)} moieties linked by a methylenediphosphonate group in the bisbidentate bridging mode. The {(VO)2(O3PCH2PO3)} core of 1 provides a fundamental structural motif for one-dimensional oxovanadium methylenediphosphonate phases. Crystal data: C23H48N2O12P2V 2: orthorhombic P22121, a = 9.767(2), b = 17.189(3), c = 20.736(4) A, V = 3481.3(12) A3, Z = 4, Dcalc = 1.35 g cm-3; structure solution and refinement based on 2022 reflections converged at R = 0.068.

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The coordination compounds of composition [VO(HL1,2)2B] (IIV) (where B = imidazole (C3 H4N2) and benzimidazole (C7H6N2); HL1: C6H5OCH2C(O)NHO1 (phenoxyacetohydroxamate), HL2: C6H5CH=CHC(O)NHO1 (cinnamohydroxamate) have been synthesized from the reactions of [VO(HL1,2)2] with equimolar amounts of imidazole and benzimidazole in ethanol. The compounds have been characterized by elemental analyses, molar conductivity, magnetic measurements, IR, UVvis, ESR, and FAB mass spectral studies. The spectral studies and molecular modeling dynamics suggest a distorted octahedral geometry around vanadium in coordination compounds. The antibacterial and antifungal activities of the newly synthesized coordination compounds, parent complexes, and respective potassium hydroxamate ligands have been screened in vitro against three bacterial strains viz. E. coli, S. aureus, and B. subtilis and two fungal strains viz. C. albicans and A. niger. The MIC values of newly synthesized coordination compounds have shown enhanced activity over parent complexes and respective potassium hydroxamate ligands. The cytotoxicity of the coordination compounds was studied on mammalian transformed cell line Hep2C, a derivative of human cervix carcinoma HeLa cells by MTT assay.

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Treatment of Boc-protected (S)-serine (Ser) methyl ester with triphenylphosphine bromide Ph3PBr (intermittently generated from PPh3 and N-bromosuccinimide) yields Boc-3-bromoalanine (R)-Boc-BrAlaMe and, after deprotection, bromoalanine methyl ester (R)-BrAlaMe in the form of its hydrobromide. Boc-BrAlaMe and BrAlaMe have been structurally characterised. The reaction between BrAlaMe, salicylaldehyde (sal) and VO 2+ results in the formation of Schiff base complexes of composition [VO(sal-BrAlaMe)solv]+ (solv = CH3OH: 3, THF: 5) and [VO(sal-BrAla)THF] 4. DFT calculations of the structures of 3, 4 and 5, based on the B3LYP functional and employing the triple zeta basis set 6-311++g(d,p), provide distances Br…V = 4.0 ± 0.1 A, if some distortion of the dihedral angle ?N-C-C-Br is allowed (affording a maximum energy of ca. 45 kJ mol-1), and thus model Br…V distances detected by X-ray methods in bromoperoxidases from the marine algae Ascophyllum nodosum and Corallina pilulifera. The DFT calculations have been validated by comparing calculated and found structures, including the new complex [V VO(Amp-sal)OMe(MeOH)] (1, Amp is the aminophenol moiety) and the known complex [VO(l-Ser-van)H2O] (van = vanillin). Additional validation has been undertaken by checking experimental against calculated (BHandHLYP) EPR spectroscopic hyperfine coupling constants. Complexes containing bromine as a substituent at the phenyl moiety of a Schiff base ligand do not allow for an appropriate simulation of the Br…V distance in peroxidases. The closest agreement, d(Br…V) = 4.87 A, is achieved with [VO(3Br-salSer)THF] (6), where 3Brsal-Ser is the dianionic Schiff base formed between 3-Br-5-NO2-salicylaldehyde and serine.

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2-Thiophenecarbanicotinic hydrazone is added with equimolar mixture of vanadyl acetyl acetonate in methanol to obtain oxovanadium(IV) complex of 2-thiophenecarbanicotinic hydrazone. Oxovanadium(IV) complex of 2-thiophenecarbanicotinic hydrazone is acted as an effective catalyst in the process. The catalytic reactions were carried under room temperature. The products generated were benzil and furil. The influence of solvent, oxidant and quantity of catalyst has been investigated. Oxovanadium(IV) complex of 2-thiophenecarba-nicotinic hydrazone proves significantly higher catalytic activity towards oxidation of secondary alcohols to ketones. The catalyst was proved to be very effective due to its recovery by simple filteration after completion of the reaction. It was reused several times which suggests that there is no change in the catalytic efficiency. Oxovanadium(IV) complex of 2-thiophenecarbanicotinic hydrazone did not show any leaching during the reaction, confirmed the heterogeneous nature.

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Two diketone based oxovanadium complexes, viz., bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionato)oxovanadium(IV) (1) and bis(1,1,1-trifluoropentane-2,4-dionato)oxovanadium(IV) (2), have been synthesized and characterized by spectroscopic and analytical techniques. The DNA binding and the cleaving ability of the complexes is assessed by UV-vis spectroscopy, fluorescence spectroscopy, viscometry and gel electrophoretic studies. The DNA binding constant values (Kb) are found to be 1.95±0.16×103M-1 for complex 1 and 1.064±0.17×103M-1 for complex 2, respectively. Based on the results of the spectral and viscosity studies, it is observed that the complexes, interestingly, have preferred minor groove binding with DNA. Further, the concentration-dependent oxidative cleavage pattern of pBR322 in the presence of the activating reagent, hydrogen peroxide, has also been discussed. In addition, the complexes have shown moderate cytotoxic activity by inducing apoptosis against the cervical cancer cell line, HeLa. The results of in silico analysis and logP predictions are found to be in good agreement with the experimental observations. Thus, synthesized oxovanadium complexes have displayed promising DNA binding behavior and DNA cleavage activity with moderately cytotoxic nature.

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Selective oxidation of cyclohexane and adamantane was performed by simple V(5+) catalyst with 1 atm O2 in acetic acid at 338-393 K. UV-vis and electron spin resonance studies suggested that peroxide species on V(5+) functioned during the oxidation. The oxidation activity was enhanced three times for cyclohexane and 6.5 times for adamantane by addition of a small amount of CF3SO3H. Copyright

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The complex [{VO(L)}2{VO(acac)}2(mu2-OMe)2] 1 can be synthesized by reaction of the Schiff base ligand N,N- bis(2-hydroxyethyl)-N’-(2-pyrrolylmethylidene)ethylenediamine (H2L) with [VO(acac)2] (Hacac = 2,4-pentanedione). The compound 1·MeOH has been characterized by IR, UV/vis, and ESR spectroscopy as well as magnetic susceptibility measurements. A single-crystal diffraction study performed on 1· MeOH gives the following crystal data: triclinic, P1 a = 7.352(2) A, b = 12.584(4) A, c = 12.826(4) A, alpha = 107.61(2), beta= 102.96(2), gamma = 95.25(2), Z = 1. The tetranuclear {(VO)4(mu3-OR)2(mu2-OR) 4}2+ core of 1 is composed of three different types of edge-shared binuclear units, an anti-coplanar, two syn-coplanar, and two twist configurations. Consistent with this connectivity pattern, analysis of the magnetic data reveals competing ferromagnetic and antiferromagnetic exchange interactions within the tetranuclear core structure. Both ESR and magnetic data indicate a singlet ground state for 1. In addition, the general magnetic behavior of oxovanadium(IV) clusters is discussed on the basis of classification schemes derived from simple binuclear fragmentation patterns. Consistent with the superexchange mechanism expected to be operative for binuclear oxovanadium(IV) units with syn-coplanar configuration, the corresponding magnetic exchange parameter Jsc of 1 (V…V = 3.410(2) A) is determined to be antiferromagnetic at -153 cm-1.

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Alkoxo-rich Schiff-bases of potentially tri-, tetra- and penta-dentate binding capacity, and their sodium tetrahydroborate-reduced derivatives, have been synthesized. Their oxo-vanadium(V) and -molybdenum(VI) complexes were synthesized and characterized using several analytical and spectral techniques including multinuclear NMR spectroscopy and single-crystal X-ray diffraction studies. Eight structurally different types of complexes possessing distorted square-pyramidal, trigonal-bipyramidal and octahedral geometries have been obtained. While VVO exhibits dimeric structures with 2-HOC6H4CH=NC(CH2OH)3 and 2-HOC6H4CH2-NHC(CH2OH)3 and related ligands through the formation of a symmetric V2O2 core as a result of bridging of one of the CH2O- groups, MoVIO gives only mononuclear complexes even when some unbound CH2OH groups are available and the metal center is co-ordinatively unsaturated. In all the complexes the nitrogen atom from a HC=N or H2CNH group of the ligand occupies a near trans position to the M=O bond. While the Schiff-base ligands act in a tri- and tetra-dentate manner in the vanadium(V) complexes, they are only tridentate in the molybdenum(VI) complexes. Proton NMR spectra in the region of bound CH2 provides a signature that helps to differentiate dinuclear from mononuclear complexes. Carbon-13 NMR co-ordination induced shifts of the bound CH2 group fit well with the charge on the oxometal species and the terminal or bridging nature of the ligand. The reactivity of the vanadium(V) complexes towards bromination of the dye xylene cyanole was studied. Transmetallation reactions of several preformed metal complexes of 2-HOC6H4CH=NC(CH2OH)3 with VO3+ were demonstrated as was selective extraction of VO3+ from a mixture of [VO(acac)2] and [MoO2(acac)2] using this Schiff base. The unusual selectivity and that of related derivatives for VO3+ is supported by binding constants and the solubility of the final products, and was established through a.c. conductivity measurements. The cis-MoO22+ complexes with alkoxo binding showed an average Mo-Oalk distance of 1.926 A, a value that is close to that observed in the molybdenum(VI) enzyme dmso reductase (1.92 A). Several correlations have been drawn based on the data.

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The ligand H2sal-cys (I) derived from salicylaldehyde and Lcysteine has been covalently bonded to chloromethylated polystyrene cross-linked with 5% divinylbenzene. Upon treatment with [VO(acac)2] in dimethylformamide (DMF) the polystyrene-bound ligand PS-H2sal-cys (II) gave the oxidovanadium(IV) complex, PS-[VO(sal-cys)·DMF] (1). The corresponding neat complex, [VO(sal-eta)]2 (2), has also been prepared similarly in methanol. These complexes have been characterised by IR, electronic, EPR spectroscopic studies, magnetic susceptibility measurements and thermal as well as scanning electron micrographs studies. Complex [VO-(sal-eta)]2 exhibits a medium intensity band at 980 cm -1 in the IR spectrum due to nu(V=O) stretch. Broad features of the EPR spectrum for the neat complex along with magnetic susceptibility studies suggest the presence of antiferromagnetic exchange interaction between two vanadium centers in close proximity. Both complexes catalyze the oxidative amination of styrene, in mild basic conditions, with secondary amines (diethylamine, imidazole, and benzimidazole) and gave a mixture of two aminated products in good yields. Amongst the two aminated products, the anti-Markovnikov product is favored over the Markovnikov one due to the steric hindrance posed by the secondary amines. The polymeranchored heterogeneous catalyst is free from leaching during catalytic action and recyclable. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

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Metal catalyst and ligand design,
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