cis-di-oxo aqua vanadium(V) | 1165951-59-6

• 英文名称: cis-di-oxo aqua vanadium(V)
• CAS: 1165951-59-6；1278585-80-0；15020-39-0；81738-79-6
• 化学式: H₈O₆V
• 分子量: 155.001
• InChiKey: MBMLLKSWGYPKBQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  meso-ΔΛ-di-μ-oxo-bis[dioxalatorhenate(IV)](4-) 、 cis-di-oxo aqua vanadium(V) 以 not given 为溶剂， 生成 perrhenate
  参考文献：
  名称：

  Mechanistic studies on the cis-[VO₂(H₂O)₄]⁺and [Mo(CN)₈]^3–oxidations of the Re^IV₂complex [(C₂O₄)₂Re(µ-O)₂Re(C₂O₄)₂]^4–

  摘要：

  Rate constants (25 degrees C) have been determined for the oxidation of the Re-2(IV), complex di-mu-oxo-bis[dioxalatorhenate(IV)]. [(C2O4)(2)Re(mu-O)(2)Re(C2O4)(2)](4-), I = 1.00 M (ClO4- or Cl-). Whereas the complex is itself stable in air at pH 7 over many days, at lower pH there is a slow decay of the 446 nm peak (epsilon = 6840 M(-1) cm(-1) per Re-2(IV)) to give in air the colourless' perrhenate(VII) [ReO4](-) product, peak at 225 nm (epsilon = 3400 M(-1) cm(-1)). The kinetics indicate a protonation step, equilibrium constant K = 2.4 M(-1), followed by the decay process k = 4.3 x 10(-5) s(-1). With the one-equivalent oxidants cis-[VO2(H2O)(4)](+) (1.0 V) and [Mo(CN)(8)](3-) (0.80 V), stoichiometries of 6 mol of oxidant per Re-2(IV) are obtained indicating conversion through to Re-VII. Two kinetic stages have been monitored with the oxidant in large excess. For the reaction with V-V as oxidant the first stage is dependent on [V-V] and [H+] as well as [Re-2(IV)], giving the rate constant k(1) = 3.31 x 10(4) M(-2) S-1. Since in the corresponding reaction with Mo-V as oxidant the reaction is independent of [H+] (k(Mo) = 2.27 x 10(4) M(-1) s(-1)), it is concluded that the V-V reactant introduces the [H+]-dependent term. The second stage of the V-V reaction gives the rate law dependence k(2obs) = k(2)[V-V] + k(0), but with the less strong Mo oxidant k(2obs) = k(0) which is approximate to 0.20 s(-1). The spectrum of the (ReReV)-Re-IV intermediate, peak at 529 nm (epsilon = 3800 M(-1) cm(-1)), was obtained by stopped-flow rapid-scan spectrophotometry. Reactions of less than full stoichiometric amounts of V-V with Re-2(IV) followed by QAE-Sephadex chromatography at 0 degrees C. gave orange-pink (peak at approximate to 495 nm) and maroon (approximate to 550 nm) intermediates, which undergo spontaneous decay.

  DOI：

  10.1039/dt9950003317
• 作为产物：
  描述：

  ammonium vanadate(V) 在 高氯酸 作用下， 以 水 为溶剂， 生成 cis-di-oxo aqua vanadium(V)
  参考文献：
  名称：

  The mechanism of oxidation of cuboidal [Mo4S4(edta)2]4− and [Mo4S4(edta)2]3− by cis-[V(O)2(H2O)4]+ and BrO3−

  摘要：

  DOI：

  10.1016/s0277-5387(00)80537-9

文献信息

• Preparation, structure and reactivity of the binuclear di-µ-oxo-bis[(ethylenediamine-N,N,N′,N′-tetraacetato)-rhenate(<scp>IV</scp>)] complex
  作者：Shinji Ikari、Tasuku Ito、William McFarlane、Mohamed Nasreldin、Bee-Lean Ooi、Yoichi Sasaki、A. Geoffrey Sykes

  DOI：10.1039/dt9930002621

  日期：——

  The dark brown dirhenium(IV) complex Ba2[Re2(mu-O)2(edta)2].4.5H2O(H4edta = ethylenediamine-N,N,N',N'-tetraacetic acid), peak at 450 nm (epsilon = 7880 M-1 cm-1 per dimer), has been prepared. From X-ray crystallography, the compound crystallizes in a monoclinic space group C2/c with a = 15.867(3), b = 12.914(2), c = 9.686(2) angstrom, beta = 123.40(1)degrees and Z = 4. The structure is centrosymmetric, with the Re atoms having distorted octahedral co-ordination, and each tetradentate edta4- ligand having two uncoordinated -CH2CO2- groups. The Re2O2 ring is planar and the short Re-Re distance of 2.362(2) angstrom is consistent with multiple metal-metal bonding. The structure is that of the meso DELTALAMBDA form. The H-1 and C-13 NMR spectra of the uncrystallised sodium salt in aqueous solution (pH 7.5) provide evidence for both meso DELTALAMBDA and racemic DELTADELTA or LAMBDALAMBDA forms. The UV-VIS and CD spectra of the (R)-pdta analogue, where pdta4- is propylenediamine-N,N,N',N'-tetraacetate, are also reported. The edta complex exhibits irreversible electrochemical behaviour with an oxidation wave at +1.23 V vs. the normal hydrogen electrode at [H+] = 0.10 M. Kinetic studies on the oxidation of the Re(IV)2 complex to Re(VII) with the one-equivalent reagent cis-[VO2(H2O)4]+ in 1 M H+ indicate a rate-determining first stage with no evidence for stable intermediate states. Effects of the product [VO(H2O)5]2+ and H+ on the kinetics, and an unexpected difference in reactivity of isomeric forms of the Re(IV)2 complex are reported.