tetracarbonyl(η2-propene)osmium | 121525-15-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: tetracarbonyl(η2-propene)osmium
• 英文别名: (η2-CH2CHCH3)Os(CO)4
• CAS: 121525-15-3
• 化学式: C₇H₆O₄Os
• 分子量: 344.322
• InChiKey: BCBCGLAEQBJGJA-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

• 作为反应物：
  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
• 作为产物：
  描述：

  十二羰基三锇 、 三聚丙烯 以 二氯甲烷 为溶剂， 以75%的产率得到tetracarbonyl(η2-propene)osmium
  参考文献：
  名称：

  s环丙烷Os（CO）4（C2H4）的结构

  摘要：

  1J(C-13-C-13) for an ethylene coordinated to Os(CO)4 has been determined as 39.0 (2) Hz from the H-1 NMR spectrum of Os(CO)4(eta2-(C2H4)-C-13). The molecular structure of Os(CO)4(eta2-C2H4) (1) has been determined by single-crystal X-ray diffraction; 1 crystallizes in space group C2/c with a = 12.271 (5) angstrom, b = 6.778 (1) angstrom, c = 12.345 (4) angstrom, beta = 129.49 (2)-degrees, V = 792.4 (2) angstrom3, and Z = 4. The geometry of 1 is approximately trigonal bipyramidal, with the ethylene carbons twisted out of the equatorial plane by 4.0-degrees. The axial carbonyls of 1 tilt toward the coordinated ethylene, with a C1-Os-C1' angle of 171.3 (5)-degrees. The optimal geometries of Os(CO)4, H2Os(CO)4, and 1 have been calculated by Hartree-Fock methods. The orbital amplitude contour diagrams of a GVB(6/12) wave function for 1 show that the axial bending occurs in order to mix in virtual p, character and improve back-bonding to the equatorial carbonyls; they also show that 1 is best described as a metallacyclopropane.

  DOI：

  10.1021/om00046a049

文献信息

• Lindner, Ekkehard; Jansen, Rolf-Michael; Hiller, Wolfgang, Chemische Berichte, 1989, vol. 122, p. 1403 - 1410
  作者：Lindner, Ekkehard、Jansen, Rolf-Michael、Hiller, Wolfgang、Fawzi, Riad

  DOI：——

  日期：——
• 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).
• Kinetics of Diosmacyclobutane Exchange Reactions
  作者：David L. Ramage、Dawn C. Wiser、Jack R. Norton

  DOI：10.1021/ja963532h

  日期：1997.6.1

  Diosmacyclobutanes Os2(CO)8(olefin) undergo facile exchange reactions with olefins and acetylenes. An associative mechanism is excluded by the observation of saturation kinetics as the concentration of the entering olefin (butyl acrylate) is increased. Multivariate analysis of the rate as a function of [C2H4] (determined from solubility measurements in decane/butyl acrylate mixtures) and [butyl acrylate]

  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。
• Structure of Os(CO)4(C2H4), an osmacyclopropane
  作者：Bruce R. Bender、Jack R. Norton、Mary M. Miller、Oren P. Anderson、A. K. Rappe

  DOI：10.1021/om00046a049

  日期：1992.10

  1J(C-13-C-13) for an ethylene coordinated to Os(CO)4 has been determined as 39.0 (2) Hz from the H-1 NMR spectrum of Os(CO)4(eta2-(C2H4)-C-13). The molecular structure of Os(CO)4(eta2-C2H4) (1) has been determined by single-crystal X-ray diffraction; 1 crystallizes in space group C2/c with a = 12.271 (5) angstrom, b = 6.778 (1) angstrom, c = 12.345 (4) angstrom, beta = 129.49 (2)-degrees, V = 792.4 (2) angstrom3, and Z = 4. The geometry of 1 is approximately trigonal bipyramidal, with the ethylene carbons twisted out of the equatorial plane by 4.0-degrees. The axial carbonyls of 1 tilt toward the coordinated ethylene, with a C1-Os-C1' angle of 171.3 (5)-degrees. The optimal geometries of Os(CO)4, H2Os(CO)4, and 1 have been calculated by Hartree-Fock methods. The orbital amplitude contour diagrams of a GVB(6/12) wave function for 1 show that the axial bending occurs in order to mix in virtual p, character and improve back-bonding to the equatorial carbonyls; they also show that 1 is best described as a metallacyclopropane.