meso-ΔΛ-di-μ-oxo-bis[dioxalatorhenate(IV)](4-) | 761343-65-1

• 英文名称: meso-ΔΛ-di-μ-oxo-bis[dioxalatorhenate(IV)](4-)
• CAS: 761343-65-1
• 化学式: C₈O₁₈Re₂
• 分子量: 756.491
• InChiKey: SQFNFXSYMPFBBG-UHFFFAOYSA-F

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