CH3ReO2(η2-O2) | 162331-68-2

• 分子结构分类: 有机化合物
• 英文名称: CH3ReO2(η2-O2)
• 英文别名: methyldioxoperoxorhenium(VII)；(methyl)ReO2(peroxo)；CH3ReO2(η-O2)；CH3Re(peroxo)O2
• CAS: 162331-68-2
• 化学式: CH₃O₄Re
• 分子量: 265.239
• InChiKey: COGCZHIFFJKGCE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.21
• 重原子数：
  6.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  59.2
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  CH3ReO2(η2-O2) 、 双氧水 以 水 为溶剂， 生成 CH3ReO(η2-O2)2(H2O)
  参考文献：
  名称：

  Deactivation of Methylrhenium Trioxide−Peroxide Catalysts by Diverse and Competing Pathways

  摘要：

  The peroxides from methylrhenium trioxide (MTO) and hydrogen peroxide, CH3ReO2(eta(2)-O-2), A, and CH3Re(O)(eta(2)-O-2)(2)(H2O), B, have been fully characterized in both organic and aqueous media by spectroscopic means (NMR and UV-vis). In aqueous solution, the equilibrium constants for their formation are K-1 = 16.1 +/- 0.2 L mol(-1) and K-2 = 132 +/- 2 L mol(-1) at pH 0, mu = 2.0 M, and 25 degrees C. In the presence of hydrogen peroxide the catalyst decomposes to methanol and perrhenate ions with a rate that is dependent on [H2O2] and [H3O+]. The complex peroxide and pH dependences could be explained by one of two possible pathways: attack of either hydroxide on A or HO2- on MTO. The respective second-order rate constants for these reactions which were deduced from comprehensive kinetic treatments are k(A) = (6.2 +/- 0.3) x 10(9) and k(MTo) = (4.1 +/- 0.2) x 10(8) L mol(-1) s(-1) at mu = 0.01 M and 25 degrees C. The plot of log ky: versus pH for the decomposition reaction is linear with a unit slope in the pH range 1.77-6.50. The diperoxide B decomposes much more slowly to yield O-2 and CH3ReO3. This is a minor pathway, however, amounting to <1% of the methanol and perrhenate ions produced from the irreversible deactivation at any given pH. Within the limited precision for this rate constant, it appears to vary linearly with [OH-] with k = 3 x 10(-4) s(-1) at pH 3.21, mu = 0.10 M, and 25 degrees C. Without peroxide, CH3ReO3 is stable below pH 7, but decomposes in alkaline aqueous solution to yield CH4 and ReO4-. As a consequence, the decomposition rate rises sharply with [H2O2], peaking at the concentration at which [A] is a maximum, and then falling to a much smaller value. Variable-temperature H-1 NMR experiments revealed the presence of a labile coordinated water in B, but supported the anhydride form for A.

  DOI：

  10.1021/ja952305x
• 作为产物：
  描述：

  双氧水 、 甲基三氧化铼(VII) 在 水 作用下， 生成 CH3ReO2(η2-O2)
  参考文献：
  名称：

  Water-Catalyzed Activation of H₂O₂ by Methyltrioxorhenium: A Combined Computational–Experimental Study

  摘要：

  The formation of peroxorhenium complexes by activation of H2O2 is key in selective oxidation reactions catalyzed by CH3ReO3 (methyltrioxorhenium, MTO). Previous reports on the thermodynamics and kinetics of these reactions are inconsistent with each other and sometimes internally inconsistent. New experiments and calculations using density functional theory with the omega B97X-D and augmented def2-TZVP basis sets were conducted to better understand these reactions and to provide a strong experimental foundation for benchmarking computational studies involving MTO and its derivatives. Including solvation contributions to the free energies as well as tunneling corrections, we compute negative reaction enthalpies for each reaction and correctly predict the hydration state of all complexes in aqueous CH3CN. New rate constants for each of the forward and reverse reactions were both measured and computed as a function of temperature, providing a complete set of consistent activation parameters. New, independent measurements of equilibrium constants do not indicate strong cooperativity in peroxide ligand binding, as was previously reported. The free energy barriers for formation of both CH3ReO2(eta(2)-O-2) (A) and CH3ReO (eta(2)-O-2)2(H2O) (B) are predominantly entropic, and the former is much smaller than a previously reported value. Computed rate constants for a direct ligand-exchange mechanism, and for a mechanism in which a water molecule facilitates ligand-exchange via proton transfer in the transition state, differ by at least 7 orders of magnitude. The latter, water-assisted mechanism is predicted to-be much faster and is consequently in much closer agreement with the experimentally measured kinetics. Experiments confirm the predicted catalytic role of water: the kinetics of both steps are strongly dependent on the water concentration, and water appears directly in the rate law.

  DOI：

  10.1021/ic401343m

文献信息

• Behaviour of dimeric methylrhenium(<scp>vi</scp>) oxides in the presence of hydrogen peroxide and its consequences for oxidation catalysis
  作者：Alexandra M. J. Rost、Andrea Scherbaum、Wolfgang A. Herrmann、Fritz E. Kühn

  DOI：10.1039/b608219j

  日期：——

  enium(VI)], slow conversion to the monomeric mono- and bis-peroxo congenes of MTO occurs. Furthermore, part of the Re(VI) starting complex is transformed into inactive perrhenate. While bis[dimethyl(μ-oxo)oxorhenium(VI)] might be applied (also in a mixture with MTO) as an oxidation catalyst precursor, (μ-oxo)bis[trimethyloxorhenium(VI)] can be applied as a useful precursor for the synthesis of tri

  避免使用有毒物质 甲基锡 合成前体 甲基三氧or （MTO）及其单和双过氧衍生物，可氧化 催化剂， 二甲基锌 可能被认为是有前途的选择 烷基化剂。但是，甲基r（VI）二聚体形成为减少 在反应过程中与MTO一起使用的产品 二甲基锌与Re 2 O 7相比，不能直接转化为环氧化催化剂在过量的H 2 O 2存在下作为MTO本身。在红色（μ-氧代）双[三甲基氧代（（VI）]的情况下，与H 2 O 2的主要反应产物是催化惰性的三甲基二氧or（VII）。在双[二甲基（μ-氧代）氧or（VI）]的情况下，会缓慢转化为MTO的单体单-和双-过氧同系物。此外，部分Re（VI）起始复合物转化为非活性的高hen酸盐。虽然可以使用双[二甲基（μ-氧代）氧or（VI）]（也可以与MTO混合使用）催化剂（μ-氧代）双[三甲基氧代（（VI）]可以用作合成下列化合物的有用前体三甲基二氧or（VII），以前只能通过不太方便的合成途径访问。
• Photolysis of CH3Re(O2)2O induced by ligand-to-metal charge transfer and by peroxide intraligand excitation
  作者：Horst Kunkely、Arnd Vogler

  DOI：10.1016/j.inoche.2005.02.014

  日期：2005.5

  The electronic spectrum of the diperoxo complex MeReVII(O-2)(2)O shows a peroxide IL (intraligand) absorption at lambda(max) similar to 260 nm in addition to the well-known peroxide to Re(VII) LMCT band at lambda(max) = 358 nm. Upon IL excitation, the diperoxo group undergoes a dismutation. Accordingly, MeRe(O-2)(2)O Photolyzes to (MeReO3)-O-VII and O-2. LMCT excitation at lambda(irr) = 405 nm is assumed to generate the radical pair MeReVII(O-2)O+/O-2(-) in the primary photochemical step. Back electron transfer and reaction with water leads finally to the monoperoxo complex MeReVII(O-2)O-2 and H2O2. (c) 2005 Elsevier B.V. All rights reserved.
• Thermal and Photochemical Reactions of Methylrhenium Diperoxide:  Formation of Methyl Hydroperoxide in Acetonitrile
  作者：Wei-Dong Wang、James H. Espenson

  DOI：10.1021/ic970650c

  日期：1997.10.1

  Compared to the system in aqueous solution, the equilibration reactions in acetonitrile between MTO and the methylrhenium peroxides CH3ReO2(eta(2)-O-2) (A) and CH3ReO(eta(2)-O-2)(2)(H2O) (B) are slower but more favored thermodynamically. In CH3CN, small concentrations of water facilitate the formation of A (especially) and B. These species decompose to methyl hydroperoxide and perrhenic acid in CD3CN, rather than to methanol and perrhenic acid as in aqueous solution. The proposed mechanism involves the intramolecular migration of the methyl group to a peroxo oxygen, followed by hydrolysis, and it is facilitated by photolysis. The potential use of B as photocatalyst does not seem promising, however.