| 50507-81-8

• CAS: 50507-81-8
• 化学式: C₁₂H₆O₆W
• 分子量: 430.026
• InChiKey: FIWDBNYEDNOXIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  、 potassium hydroxide 在 potassium chloride 作用下， 以 水 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Physical Organic Chemistry of Transition Metal Carbene Complexes. 21.¹ Kinetics and Mechanism of Hydrolysis of (CO)₅MC(SR)Ar (M = Cr and W; R = CH₃ and CH₃CH₂CH₂; Ar = C₆H₅ and 3-ClC₆H₄) in Aqueous Acetonitrile. Important Differences Relative to Complexes with Alkoxy Leaving Groups

  摘要：

  A kinetic study of the hydrolysis of (CO)(5)M=C(SMe)Ph (M = Cr and W) in 50% MeCN-50% water (v/v) at 25 degreesC over a pH range from 1.7 to 14.2 is reported. The reaction occurs in two stages: the first is formation of (CO)(5)M=C(O-)Ph or (CO)(5)M=C(OH)Ph while the second stage leads to the formation of PhCH=O and (CO)(5)MOH-. This paper is concerned with the first stage. The rate-pH profiles are complex and consistent with a mechanism (Scheme 1) that involves water/OH- addition to the substrate to form a tetrahedral intermediate (T-OH(-)), followed by product formation via five potential pathways whose relative importance depends on the pH. A more limited study of the reactions of (CO)(5)M=C(SCH2CH2CH3)Ph (M = Cr and W) and (CO)(5)M=C(SMe)C6H4-3-Cl (M = Cr and W) with OH- is also reported. The main focus of the discussion is aimed at understanding the reactivity differences between (CO)(5)M=C(SMe)Ph and the corresponding methoxy analogues studied earlier. This understanding is in large measure based on an analysis of how the intrinsic rate constants are affected by the interplay of steric, inductive, and pi -donor effects and the potential imbalances of these effects at the transition state. It is also shown that the much lower sensitivity to H+-catalysis of RS- compared to RO- leaving group departure from the tetrahedral intermediate is responsible for the more complex rate-pH profile for the hydrolysis of (CO)(5)M=C(SMe)Ph than for the hydrolysis of the methoxy analogue.

  DOI：

  10.1021/ja002371l

文献信息

• Physical Organic Chemistry of Transition Metal Complexes. 31. Nucleophilic Attachment of the Malononitrile Anion to Fischer Carbene Complexes
  作者：Claude F. Bernasconi、Mahammad Ali

  DOI：10.1021/om0401051

  日期：2004.12.1

  CH(CN)2- to Fischer carbene complexes of the type (CO)5MC(XR)C6H4Z with M = Cr, W and XR = OMe, OEt, SMe in 50% MeCN−50% water (v/v) at 25 °C are reported. The malononitrile anion shows a much higher reactivity toward these carbene complexes than OH-, primary aliphatic amines (e.g. n-butylamine), or secondary alicyclic amines (e.g. piperidine) but is slightly less reactive than thiolate ions (e.g.

  速率常数为CH的附接（CN）2 -的式（CO）的费歇尔卡宾络合物5中号C（XR）C 6 H ^ 4，其中M =的Cr，W和XR = OME，OET，中小型50％Z据报道在25°C时MeCN-50％水（v / v）。丙二腈阴离子节目朝向这些卡宾络合物比OH高得多的反应性- ，脂族伯胺（例如Ñ丁胺），或仲脂环胺（例如哌啶），但略大于硫醇盐离子（例如HOCH反应性较低的2 CH 2小号-）。烷氧基卡宾配合物的反应比硫代甲基衍生物更快，这与先前对烷氧化物离子OH的发现一致-，胺和硫醇盐离子亲核试剂。与（CO）5 Cr C（SMe）C 6 H 4 Z反应的Hammettρ值为0.69，与（CO）5 Cr C（OMe）C 6 H 4 Z反应的Hammettρ值为2.88 。甲氧基卡宾配合物与以前在其他亲核试剂中观察到的模式相吻合，可以用甲氧基的π-给体效应来解释，该效应要比硫代甲基强得多。