• Title/Summary/Keyword: Oxovanadium(IV) complexes

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Magnetic and Spectroscopic Studies of some Oxovanadium(IV) Complexes having O = V(O)$_4$ Chromophore

  • Choi, Sung-Nak;Kim, Young-Inn;Shim, Yoon-Bo;Choo, Hi-Shik;Kim, Young-Jin
    • Bulletin of the Korean Chemical Society
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    • v.10 no.2
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    • pp.138-142
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    • 1989
  • Three oxovanadium(IV) complexes with bidentate ligands having only oxygen donor atoms, benzohydroxamic acid (Hben), 8-hydroxyquinoline-N-oxide(Hhqno) and picolinic acid-N-oxide (Hpicn) are prepared and magnetic and spectroscopic properties are investigated for the complexes $VO(ben)_2,\;VO(hqno)_2\;and \;VO(picn)_2.$ Magnetic data together with IR results strongly indicate that dimeric intermolecular interaction is significant in $VO(ben)_2$ while the presence of polymeric V-O${\cdot}{\cdot}$V-O interaction is suggestive in $VO(picn)_2$. For all three complexes, three electronic d-d transitions were observed; extremely strong optical absorption of these bands of $VO(ben)_2$ in DMSO are supposed to be arised from a great metal-ligand covalency. Some fundamental vibration modes of oxovanadium(IV) complexes were empirically assigned from the differences in the spectrum of metal complexes with free ligand.

Vanadyl Binary Schiff Base Complexes Containing N2O2 Coordination Sphere: Synthesis, Ab Initio Calculations and Thermodynamic Properties

  • Asadi, Mozaffar;Ghatee, Mohammad Hadi;Torabi, Susan;Mohammadi, Khosro;Moosavi, Fatemeh
    • Journal of the Korean Chemical Society
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    • v.57 no.1
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    • pp.63-72
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    • 2013
  • Some vanadyl complexes were synthesized by treating a methanolic solution of the appropriate Schiff base ligand and one equivalent of $VO(SO_4)_2$ to yield [($VOL_2^{1-14}$)](L=Salicylaldehyde's derivatives, Schemes 1, 2). These oxovanadium (IV) complexes were characterized based on their FT-IR, UV-Vis spectroscopy and elemental analysis. The IR spectra suggest that coordination takes place through azomethine nitrogen and phenolate oxygen. In addition, the formation constants of the oxovanadium (IV) binary complexes were determined in methanolic medium. The ab initio calculations were also carried out to determine the structural and the geometrical properties of one of the complexes and its calculated vibrational frequencies were investigated.

Electrochemical Studies of Oxovanadium(IV) Complex of 2-Amino-1-cyclopentene-1-dithiocarboxylate

  • Young-Jin Kim;Duck-Soo Park;Yoon-Bo Shim;Sung-Nak Choi
    • Bulletin of the Korean Chemical Society
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    • v.11 no.2
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    • pp.89-94
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    • 1990
  • The redox properties of 2-amino-1-cyclopentene-1-dithiocarboxylate anion (acdc) and its oxovanadium complex, $VO(acdc)_2$ have been investigated in dimethylformamide (DMF) with polarography and cyclic voltammetry. Bis(2-amino-1-cyclopentene-1-dithiocarboxylate) oxovanadium(IV) exhibits two polarographic oxidation waves and two reduction waves in the potential range from +0.50V to - 2.4V vs. the Ag/AgCl (DMF) reference electrode. The second oxidation wave appeared at - 0.08V is found to be reversible and is attributed to the formation of $VO(acdc)_2\;^+$. The first reduction process (at - 0.60V) is also reversible and this reduction process is caused by the electrode process of formation of $VO(acdc)_2$-species. The half wave potential for the reduction, V(IV)$\to$V(III) is more positive for oxovanadium complexes containing sulfur donor atoms than other VO(IV) complexes having oxygen or nitrogen donor atoms.

Oxovanadium(IV) Complexes Containing VO(ONS) Basic Core: Synthesis, Structure, and Spectroscopic Properties

  • Jang, Yoon-Jung;Lee, Uk;Koo, Bon-Kweon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.72-76
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    • 2005
  • Some mononuclear oxovanadium(IV) complexes having the general formula [VOL(bidentate)] (1-4) of which L is tridentate ONS-donor salicylaldehyde S-methyldithiocarbazate (sal-mdtc$^{2-}$) or salicylaldehyde 4- phenylthiosemicarbazate (sal-phtsc$^{2-}$) and bidentate stands for 2,2'-bipyridyl (bpy) or 1,10-phenanthroline (phen) have been synthesized. The complexes were characterized by elemental analyses, FAB mass, UV, IR spectroscopy, and cyclic voltammetry. Two of the complexes [VO(sal-mdtc)(bpy)] (1) and [VO(sal-mdtc) (phen)] (2) were crystallographically characterized. The structures revealed that vanadium atom is octahedrally coordinated by the O, N, and S donor atoms of the tridentate ligand, the two N atoms of bidentate ligand, and the oxo atom. The oxygen donor, occupying an apical position has a trans-labilizing effect, resulting in elongation of the V-N bond. The cyclic voltammograms of the complexes exhibited one cathodic response in the range −d1.45 $\sim$ −f1.52 V due to the reduction of V(IV) to V(III).

Magnetic and Infrared Spectral Studies of Oxovanadium (IV)-Carboxylate Complexes (옥소바나듐 (IV)-카르복실레이트 착물의 자기적 및 적외적 분광학적 성질)

  • Yoon-Bo Shim;Sung-Nak Choi;Jong-Yul Park
    • Journal of the Korean Chemical Society
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    • v.30 no.1
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    • pp.76-83
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    • 1986
  • Four oxovandium(IV) complexes with carboxylate ligands, $VO(picn)_2$, $VO(htmq)_2$, $VO(quin)_2$ and $VO(pyra)_2{\cdot}2H_2O)$ have been prepared and studied. Infrared spectral data coupled with the results of magnetic susceptibility study strongly suggest that there are relatively strong intermolecular interactions in $VO(picn)_2$ and $VO(htmq)_2$. In all oxovanadium(IV) complexes studied in this work, the carboxylate ligand coordinates to the metal ion in the unidentated fashion. Some fundamental vibration modes of oxovanadium(IV) complexes were empirically assigned from the difference in the spectrum of metal complex with free ligand.

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Polarographic Behavior of Oxovanadium (IV) Complex of Mercaptopyridine N-Oxide

  • Shim, Yoon-Bo;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.225-230
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    • 1987
  • The redox properties of 2-mercaptopyridine N-oxide (mpno) and its oxovanadium complex, $VO (mpno)_2$ have been studied by the use of polarography and cyclic voltammetry. The radical anion of mpno is generated in acetone and is adsorbed to the electrode to form an adsorption wave at -0.21 V vs Ag/AgCl electrode. The normal wave appeared at -0.50 V is attributed to the formation of radical anion. The $VO (mpno)_2$ exhibits one oxidation wave at +0.57 V, and two reduction waves at -1.07 V and -1.76 V vs. Ag/AgCl electrode; the oxidation is fully reversible one-electron process ($VO (mpno)_2\;{\leftrightarrow}\;VO(mpno)_2^+ + e).$ The reduction wave at -1.07 V is quasireversible and is arised from the formation of $VO (mpno)_2^-.$ The second reduction wave at -1.76 V is irreversible and this reduction process consists of two one-electron steps. The sulfur containing ligands seem to enhance the stability of lower oxidation state of vanadium while the oxygen or nitrogen donor of the ligands stabilize the higher oxidation state of vanadium when comparisons are made among several oxovanadium complexes.

Synthesis and Characterization of Metal Complex Oxo Vanadium(Ⅳ) Complexes with Derivatives of Salicylaldoximes (옥심계 금속착물의 합성과 그 물성에 관한 연구 치환 살리실알데히드옥심의 바나듐(Ⅳ) 착물(1))

  • Lee, Kwang;Lee, Won Sik
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.611-616
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    • 1995
  • Oxovanadium(IV) complexes with salicylaldoxime, o-vanilline oxime, 2-hydroxy-4-methoxybenzaldoxime, 2-hydroxy-5-methoxybenzaldoxime and 2-hydroxy-5-nitrobenzaldoxime were synthesized. The complexes have been characterized by elemental analysis, electric conductivity measurement, infrared spectrometry, electronic spectrometry, mass spectrometry, and thermal analysis. The results of elemental analysis were well coincided with the theoretical values. The values of molar conductance of the complexes in DMF implicated that the complexes were non-electrolyte. The characteristic stretching frequency of V=O appeared strong band in the range of $980{\pm}20\;cm^{-1}.$ All the complexes showed two d-d transition in visible spectra and two charge transfer transitions in ultraviolet spectra. Results of mass spectrometry of $VO(sal)_2\;and\;VO(van)_2$ indicated two peaks corresponding to vanadium containing ion(I) of 1 : 2(metal to ligand) chelate and a fragment ion(II) of 1 : 1 chelate due to loss of ligand radical from ion(I). The thermal analysis showed the endothermic peak due to the thermal decomposition.

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Electrochemical Behavior of Oxovanadium (IV) Complex of Benzohydroxamic Acid (옥소바나듐 (IV) 과 벤조히드로옥사믹산 간에 형성되는 착물의 전기화학적 성질에 관한 연구)

  • Hi Sik Choo;Duk Soo Park;Yoon Bo Shim;Sung Nak Choi
    • Journal of the Korean Chemical Society
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    • v.33 no.3
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    • pp.281-286
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    • 1989
  • The redox properties of benzophydroxamic acid (Hben) and its oxovanadium complex, $VO(Ben)_2$ has been studied by the use of polarograpy and cyclic voltammetry. The radical anions of Hben seem to be generated in acetone. The wave at -0.05V vs. Ag/AgCl electrode might be attributed to the formation of radical anion and the wave at -1.78V vs. Ag/AgCl electrode might be attributed the formation of radical dianion. The $VO(Ben)_2$ exhibits one oxidation wave at + 0.55V and two reduction waves at -0.15V and -1.30V vs. Ag/AgCl electrode; the oxidation is reversible one electron process $(VO(ben)_2 {\rightleftharpoons} VO(ben)^+ + e)$. The reduction wave at -0.15V is quasireversible and is arised from the formation of radical anion,$VO(Ben)_2^-$. The second reduction wave at -1.30V is irreversible and this reduction process produces vanadium(III). This oxygen containing ligand of Hben seems to reduce the stability of + 4 oxidation state of vanadium while the sulfur or nitrogen donor of the ligands stabilize the + 4 oxidation state of vanadium when comparisons are made among several oxovanadium complexes.

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