methyltrioxorhenium(VII)-d3 | 112440-06-9

• 分子结构分类: 有机化合物
• 英文名称: methyltrioxorhenium(VII)-d3
• 英文别名: methyltrioxorhenium(VII)；methyltrioxorhenium
• CAS: 112440-06-9
• 化学式: CH₃O₃Re
• 分子量: 252.216
• InChiKey: PQTLALPZRPFYIT-HCUZFQMISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.22
• 重原子数：
  5.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  51.21
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyltrioxorhenium(VII)-d3 以 solid matrix 为溶剂， 生成
  参考文献：
  名称：

  Matrix Photochemistry of Methyltrioxorhenium(VII), CH₃ReO₃:  Formation of the Methylidene Tautomer H₂CRe(O)₂OH and Its Potential Relevance to Olefin Metathesis

  摘要：

  IR spectroscopic measurements:have been used to chart the reactions activated by irradiating argon matrices doped with methyltrioxorhenium, CH3ReO3 (1), first with light sit wavelengths near 254 nm and subsequently with broad-band UV-visible light (200 less than or equal to lambda less than or equal to 800 nm). Assignments of the IR absorption bands are made and. their carriers identified on the basis of experiments with CD3ReO3 or (CH3ReO3)-C-13 and by comparison either with the vibrational. properties forecast by density functional theory (DFT) calculations or with those of related molecules. Photoexcitation at lambda = ca. 254 nm results in tautomerization of CH3ReO3 to the methylidene derivative H2C=Re(O)(2)OH (2), the properties of which have been determined, partly by experiment and partly by DFT calculations. The mechanism of the change is discussed, as is the relevance of the tautomeric product to the catalytic action of CH3ReO3 in olefin metathesis. Broad-band UV-visible radiation leads to the formation of a rhenium carbonyl, 3, possibly the Re(V) compound H2Re(CO)(O)OH.

  DOI：

  10.1021/om0100479
• 作为产物：
  描述：

  rhenium(VII) oxide 在 Sn(CD₃)4 作用下， 以 四氢呋喃 为溶剂， 生成 methyltrioxorhenium(VII)-d3
  参考文献：
  名称：

  Herrmann, Wolfgang A.; Kuchler, Josef G.; Felixberger, Josef K., Angewandte Chemie, 1988, vol. 100, p. 420 - 422

  摘要：

  DOI：

文献信息

• Proton−Deuteron Exchange Reactions of Methyltrioxorhenium(VII) in Organic Solvents
  作者：Mitsuru Matsumoto、James H. Espenson

  DOI：10.1021/om049029s

  日期：2005.5.1

  same treatment applies to the methanol-d4/lutidine system in benzene-d6, once allowance is made for formation of an MTO−methanol adduct. Reasonably rapid exchange under mild conditions reflects the acidic character of MTO, which may arise from its base-promoted keto/enol tautomerization. Three consecutive steps are suggested for the reaction mechanism:  attack of a base on an MTO methyl proton, isomerization

  甲基三氧H（VII）（MTO）的质子/氘化（H / D）交换的速率常数在四种有机溶剂中通过时程1 H NMR测量确定。MTO和氘供体之间的交换仅在存在路易斯碱的情况下进行。该反应不会在中性或酸化的溶液中发生。动力学取决于碱，氘供体和溶剂。所观察到的伪一级速率常数（ķ ψ当使用配位的碱，但与非配位的碱增加）是小到可以忽略。有直接的关系被发现之间ķ ψ和p ķ一个的碱基的共轭酸的值。与苯酚-d 6作为氘给体（d）和2,6-二甲基吡啶作为碱（B），速率法用溶剂而异：  ķ ψ = ķ一个[d] [B]在苯d 6（ķ一个= 1.95×10 - 3 kg的2摩尔- 2个小号- 1）;  ķ ψ = ķ一个κ[d] [B] /（1 +κ[d]）在氯仿d（ķ一个= 1.41×10 - 2 kg的摩尔- 1个小号- 1，κ=0.79公斤摩尔- 1）; ķ ψ = ķ一个[B]在丙酮d 6和乙腈d 3（ķ一个=
• Alkylrhenium oxides as homogeneous epoxidation catalysts: Activity, selectivity, stability, deactivation
  作者：Wolfgang A. Herrmann、Richard W. Fischer、Monika U. Rauch、Wolfgang Scherer

  DOI：10.1016/0304-5102(93)e0162-a

  日期：1994.1

  Methyltrioxorhenium(VII) (MTO, 1a) and several congeners 1b and 2a-d of formula RReO3 and RReO3·L, respectively, qualify as olefin epoxidation catalysts of high activity and selectivity. Related alkylrhenium (VI) complexes form efficient catalyst precursors as well, since they get oxidized by H2O2 to the same active species CH3ReO(O2)2·H2O (3). The present paper presents a comparison of this novel

  甲基三（VII）（MTO，1A）和几个同源1B和图2a-d式RReO 3和RReO 3 ·L，分别有资格作为高活性和选择性的烯烃环氧化的催化剂。相关的烷基hen（VI）配合物也形成有效的催化剂前体，因为它们被H 2 O 2氧化为相同的活性物质CH 3 ReO（O 2）2 ·H 2 O（3）。本文介绍了这种新型催化剂与已知常用催化剂的性能的比较。记录了催化剂的稳定性并描述了失活反应。（浅粉红色）单体氨基官能化复合物O 3（C 2 H 5）2（4A及其（紫色）聚合物形式（4B）的合成和晶体结构（X射线衍射）得到了报道。后者是具有H 2 O 2的活性环氧化催化剂，描述了标准催化剂MTO 1a的改进的实验室方法。
• Essays über Metallorganische Chemie V. Stand und Aussichten der Rhenium-Chemie in der Katalyse
  作者：Wolfgang A. Herrmann

  DOI：10.1016/0022-328x(90)85211-g

  日期：1990.2

  transition metal compounds as oxidation catalysts [2]: “The catalytic activity of technetium seems to be comparable to that of rhenium …, and both seem to be low.” The present account briefly describes the status of rhenium chemistry in catalysis, showing that there are many more perspectives than were first believed. It is shown that high-valent organorhenium oxides function as very effective catalysts

  关于催化环氧化反应的最新评论文章颇为令人沮丧的说法是，较重的VII族过渡金属化合物作为氧化催化剂[2]：“ of的催化活性似乎可与of相媲美，而both的催化活性似乎与rh相当。低的。” 本报告简要描述了化学在催化中的状态，表明与人们最初认为的观点相比，存在更多的观点。结果表明，高价有机or氧化物在烯烃复分解（非均相催化）和烯烃氧化（均相催化）中均起非常有效的催化剂的作用。在此内容中，很明显，与相邻元素钨和相比，对化学的研究和了解通常要少得多。此外，与tech化合物有关的工作是必要的，以便更好地了解相应rh化合物的催化和其他性能。除了已知的tech和inorganic之间的无机和配位化合物关系外，
• Herrmann, Wolfgang A.; Fischer, Richard W., Journal of the American Chemical Society, 1995, vol. 117, # 11, p. 3223 - 3230
  作者：Herrmann, Wolfgang A.、Fischer, Richard W.

  DOI：——

  日期：——