| 189890-37-7

• CAS: 189890-37-7
• 化学式: C₁₁H₁₂O₆Os
• 分子量: 430.413
• InChiKey: XFGBRPQVPOLMBI-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：

  tetracarbonyl(η2-propene)osmium 、 丙烯酸丁酯 以 癸烷 为溶剂， 生成
  参考文献：
  名称：

  Diosmacyclobutane 交换反应的动力学

  摘要：

  Diosmacyclobutanes Os2(CO)8(烯烃) 与烯烃和乙炔发生容易的交换反应。随着进入的烯烃（丙烯酸丁酯）的浓度增加，通过观察饱和动力学排除了相关机制。作为 [C2H4]（由癸烷/丙烯酸丁酯混合物中的溶解度测量确定）和 [丙烯酸丁酯] 的函数的速率的多变量分析表明了一种逐步机制，其中离开的烯烃迁移到末端位置，然后与进入烯烃。Os(CO)4(烯烃)中烯烃配体的直接解离交换显示在低得多的进入烯烃浓度下饱和。

  DOI：

  10.1021/ja963532h

文献信息

• Evidence for a Ring-Opening Preequilibrium in the Exchange Reactions of Diosmacyclobutanes
  作者：Bruce R. Bender、David L. Ramage、Jack R. Norton、Dawn C. Wiser、Anthony K. Rappé

  DOI：10.1021/ja963533+

  日期：1997.6.1

  Variable-temperature C-13 NMR does not show any evidence for intramolecular ethylene rotation in 1-C-13. The rates of alkene dissociation for the propene (8) and trans-2-butene (7) adducts of Os-2(CO)(8) have been measured in hydrocarbon solution and compared with the rates of alkene dissociation from the corresponding Os(CO)(4)(alkene) adducts 6 and 9. The kinetic labilities of propene and trans-2-butene are reversed in the Os-2(CO)(8)(alkene) and Os(CO)(4)(alkene) systems; propene is replaced 2.5 times faster than trans-2-butene in the Os-2(CO)(8)(alkene) system, while trans-2-butene is replaced 55.9 times faster than propene in the Os(CO)(4)(alkene) system. We have used molecular mechanics to explore the reasons for this unusual reactivity pattern and have found that these results may be easily reconciled with a ring-opening mechanism for alkene replacement in the Os-2(CO)(8)(alkene) system. We have confirmed that alkene exchange with Os(CO)4(alkene) is dissociative, in agreement with precedent. The secondary deuterium kinetic isotope effect (KIE) has been measured for the replacement of C2H4 and C2D4 in Os-2(CO)(8)(mu-eta(1),eta(1)-C2H4) (1) and Os-2(CO)(8)(mu-eta(1),eta(1)-C2D4) (1-d(4)); it is 1.30(1) at 39 degrees C. The measured KIE is consistent with a ring-opening associative mechanism for alkene exchange (mechanism II in the previous paper).