CH3ReO(η2-O2)2(H2O) | 152385-10-9

• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 过渡金属有机体
• 英文名称: CH3ReO(η2-O2)2(H2O)
• 英文别名: methy(oxo)bis(η(2)-peroxo)rhenium(VII)；[CH3Re(O)(η(2)-O2)2(OH2)]；CH3Re(O)(η(2)-O2)2(OH2)；[MeReO(κ2-O2)(OH2)]；(methyl)ReO(water)(peroxo)2；CH3ReO(η-O2)2(H2O)
• CAS: 152385-10-9
• 化学式: CH₅O₆Re
• 分子量: 299.254
• InChiKey: GVXUQATXNFVSEG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  CH3ReO(η2-O2)2(H2O) 以 not given 为溶剂， 生成 Rhenium, methyloxodiperoxy-
  参考文献：
  名称：

  有机金属化学论文，七。昨天的实验室好奇心，明天的催化剂：有机金属氧化物

  摘要：

  organorhenium-和有机锇氧化物的系统的调查，以下三氧代的初始发现（η 5 -五甲基）铼（VII）在1984年由赫尔曼，塞拉诺和烈性黑啤酒，已经产生了高氧化态的有机金属化合物的过多。关键化合物甲基三氧or（VII）现在很容易获得，并且显示出令人惊讶的广泛催化活性，尤其是在烯烃复分解，烯烃环氧化和芳族氧化（维生素K 3）。在这种情况下，解决并解决了与合成和反应性，结构和键以及热和光化学稳定性有关的一般问题。有机金属氧化物也可以用作结构明确的分子或聚合物前体化合物，用于合成无机氧化物，三氧化rh的形成是由聚合物途径产生的第一个例子。

  DOI：

  10.1016/0022-328x(95)00518-u
• 作为产物：
  描述：

  甲基三氧化铼(VII) 在 高氯酸 、 urea hydrogen peroxide 作用下， 以 水 为溶剂， 生成 CH3ReO(η2-O2)2(H2O)
  参考文献：
  名称：

  Comparative kinetic investigations in ionic liquids using the MTO/peroxide system

  摘要：

  The kinetics and thermodynamics of the reaction of methyltrioxorhenium (MTO) with hydrogen peroxide in ambient temperature ionic liquids have been studied. The rate constant for the formation of the diperoxorhenium complex, CH3ReO(eta(2)-O-2)(2), from the monoperoxorhenium complex, CH(3)Reo(2)(eta(2)-O-2), and hydrogen peroxide in [bmim]NO3 is 0.053 +/- 0.002 M-1 s(-1). The equilibrium constants for the binding of two peroxide units have been determined in [emim]BF4 to be K-1 = 110 +/- 28 and K-2 = 160 +/- 36. Similar rate constants and equilibrium constants are obtained in other water-miscible, dialkylimidazolium and alkylpyridinium ionic liquids. The values of the rate constants are highly dependent on the concentration of water in the solvent. These results indicate that the ionic liquids can behave like organic solvents and aqueous solutions of high salt concentrations. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s1381-1169(02)00236-4

文献信息

• Mehrfachbindungen zwischen hauptgruppenelementen und Übergangsmetallen. 158. Photochemische und photophysikalische Eigenschaften des epoxidierungskatalysators CH3ReO(O2)2·H2O
  作者：Ioannis Hatzopoulos、Hans-Dieter Brauer、Martin R. Geisberger、Wolfgang A. Herrmann

  DOI：10.1016/0022-328x(96)06309-7

  日期：1996.8

  The photolysis of CH3ReO(O2)2·H2O in methylene chloride yields, like the thermolysis, molecular oxygen in the triplet spin state. The quantum yield QPh of photolysis shows a remarkable dependence the wavelength, increasing from 0.12 at 365 nm to 1.0 at 248 nm. One single excited state is responsible for this behaviour. The wavelength-dependent quantum yield profile corresponds in a first approximation

  CH 3 ReO（O 2）2 ·H 2 O在二氯甲烷中的光解产生三重态自旋状态的分子氧，就像热分解一样。光解的量子产率Q Ph显示出显着的波长依赖性，从365 nm的0.12增加到248 nm的1.0。一个单一的激发态对此行为负责。波长相关的量子产率曲线在第一近似中对应于LMCT带和总吸收光谱之间的比率，该比率是在数学基础上使用对称高斯曲线得出的。这是d 0的烷基过渡金属配合物的荧光和磷光发射首次已经检测到-构型，因此允许确定S 1和T 1-能级。荧光（Q F）的量子产率低于10 -3 ; 磷光的值低于0.04。
• Multiple bonds between transition metals and main-group elements: Part 16111Communication 160 of this Series: M.H.P. Rietveld, L. Nagelholt, D.M. Grove, N. Veldman, A.L. Spek, M.U. Rauch, W.A. Hermann, G. van Koten, J. Organomet. Chem. (1996), in press. Oxygen-donor adducts of organorhenium(VII) oxides: syntheses, structures and catalytic properties
  作者：Wolfgang A. Herrmann、João D.G. Correia、Monika U. Rauch、Georg R.J. Artus、Fritz E. Kühn

  DOI：10.1016/s1381-1169(96)00377-9

  日期：1997.4

  N-Oxide adducts of methyltrioxorhenium(VII) (1) are characterized and their catalytic properties in the epoxidation of olefins with hydrogen peroxide are examined. The crystal structure of one of these derivatives is described. Whereas aliphatic N-oxides form temperature-sensitive adducts with 1 and are inactive in the catalytic epoxidation of olefins, aromatic N-oxides adducts of 1 are both stable and

  表征了甲基三氧杂ium（VII）（1）的N-氧化物加合物，并研究了它们在烯烃与过氧化氢环氧化中的催化性能。描述了这些衍生物之一的晶体结构。脂族N-氧化物与1形成对温度敏感的加合物，并且在烯烃的催化环氧化中不活泼，而芳族N-氧化物1的加合物既稳定又具有催化活性。后者的络合物​​显示出比1低的活性，但在某些情况下，其选择性甚至高于1的N基加合物的选择性。。在所有检查的情况下，催化活性物质均为相似类型。报道了羰基官能化配合物[O 3 Re（CH 2）2 CH（CH 3）OCH 3 ]的结构及其在烯烃过氧化氢环氧化中的催化性能。还检查了该催化剂的失活过程。
• Oxidations of ER3 (E = P, As, or Sb) by Hydrogen Peroxide: Methylrhenium Trioxide as Catalyst
  作者：Mahdi M. Abu-Omar、James H. Espenson

  DOI：10.1021/ja00106a030

  日期：1995.1

  Catalytic and noncatalytic conversions of tertiary phosphines to their oxides by hydrogen peroxide have been investigated. The catalyst is methylrhenium trioxide, CH[sub 3]ReO[sub 3]. The kinetics were investigated in acetonitrile-water (1:1 by volume) at 25[degree]C. Stepwise interactions between CH[sub 3]ReO[sub 3] and H[sub 2]O[sub 2] form CH[sub 3]Re([eta][sup 2]-O[sub 2])(O)[sub 2](OI[sub 2])

  已经研究了通过过氧化氢将叔膦催化和非催化转化为它们的氧化物。催化剂是三氧化甲基铼，CH[sub 3]ReO[sub 3]。在 25°C 下在乙腈-水（体积比为 1:1）中研究动力学。CH[sub 3]ReO[sub 3]和H[sub 2]O[sub 2]之间的逐步相互作用形成CH[sub 3]Re([η][sup 2]-O[sub 2])(O)[子 2](OI[子 2])。A，和 CH[sub 3]Re([η][sup 2]-O[sub 2])[sub 2](O)(OH[sub 2])，B。在 CH[sub 3]CN-H [sub 2]O (1:1 v/v) 平衡常数为 K[sub 1] = 13 [+-] 2 L mol[sup [minus]1] 和 K[sub 2] = 136 [+-] 28 L mol[sup [minus]1] 在 pH 1.0 和 25°C。在该介质中形成 A
• Multiple bonds between main group elements and transition metals, 155. (Hexamethylphosphoramide) methyl(oxo) bis(η2-peroxo)rhenium(VII), the first example of an anhydrous rhenium peroxo complex: crystal structure and catalytic properties
  作者：Wolfgang A. Herrmann、João D.G. Correia、Georg R.J. Artus、Richard W. Fischer、Carlos C. Romão

  DOI：10.1016/0022-328x(96)06272-9

  日期：1996.8

  Methyl(oxo)bis(η2-peroxo)rhenium(VII)1, the active species of the system CH3ReO3/H2O2 in the catalytic oxidation of different organic and organometallic compounds, is stabilized by a water molecule attached to the rhenium center. This water molecule can be removed and substituted by hexamethylphosphoramide (HMPA) to yield (hexamethylphosphoramide)methyl(oxo)bis(η2-peroxo rhenium(VII) (3). The synthesis

  甲基（氧代）双（η 2 μ-过氧）铼（VII）1，系统CH的活性种3 REO 3 / H 2 ö 2在不同的有机和有机金属化合物的催化氧化，通过水分子稳定的固定到the中心。该水分子可以被移除并且由六甲基磷酰胺（HMPA）取代，得到（六甲基磷酰胺）甲基（氧代）双（η 2 μ-过氧铼（VII）（3）。合成，晶体结构（X射线difraction研究），和报告了该化合物的催化特性，晶体数据如下：单斜晶系，空间群P 2 1/ n，a = 900.76（7）pm，b = 1229.80（11）pm，c = 1318.57（11）pm，β = 90.251（7）°，R w = 0.034（1878次反射）。化合物3在H 2 O 2氧化烯烃的催化性能与1相似。
• Deactivation of Methylrhenium Trioxide−Peroxide Catalysts by Diverse and Competing Pathways
  作者：Mahdi M. Abu-Omar、Peter J. Hansen、James H. Espenson

  DOI：10.1021/ja952305x

  日期：1996.1.1

  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.