1,2-eq,eq-[Re2(THF)2(CO)8] | 213201-71-9

• 英文名称: 1,2-eq,eq-[Re2(THF)2(CO)8]
• CAS: 213201-71-9
• 化学式: C₁₆H₁₆O₁₀Re₂
• 分子量: 740.711
• InChiKey: AUZKEVGTVXXXAW-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：

  1,2-eq,eq-[Re2(THF)2(CO)8] 、 二氯甲烷 以 二氯甲烷 为溶剂， 生成 [Re2(μ-H)(μ-Cl)(CO)8]
  参考文献：
  名称：

  1,2-eq,eq-[Re₂(CO)₈(THF)₂]:  A Reactive Re₂(CO)₈ Fragment That Easily Activates H−H and C−H Bonds

  摘要：

  The reaction of [Re-2(mu-H)(2)(CO)(8)] (1) with diazomethane at 193 K in THF-d(8) gives the unstable [Re-2(mu-H)(mu-CH3)(CO)(8)] derivative (2) containing a methyl group arising from the insertion of CH2 into a Re-H-Re bond. Isotopic perturbation of the equilibria by partial deuteration demonstrated that the methyl bridges the Re-Re bond in an unsymmetrical way, with a fast exchange between one agostic and two terminal C-H bonds. At temperatures higher than 253 K, 2 decomposes, in THF solution, with CH4 elimination to give the novel red complex 1,2-eq,eq-[Re-2(CO)(8)(THF)(2)] (3), which was characterized by NMR spectroscopy and X-ray analysis. In the solid form a staggered conformer of Ca symmetry was found. C-13 NMR analysis revealed the presence, in wet THF, of the aquo complexes [Re-2(CO)(8)(THF)(H2O)] (4) and [Re-2(CO)(8)(H2O)(2)] (5), whose formation is favored at low temperature (Delta H degrees for the formation of 5 from 4: -14.4(2) kJ mol(-1)). In solution, due to the lability of the THF ligands, 3 behaves as a "lightly stabilized" Re-2(CO)(8) fragment, capable of activating different E-H bonds. Reaction with HCl in THF leads to [Re-2(mu-H)(mu-Cl)(CO)(8)], while with H-2 the unsaturated starting material [Re-2(mu-H)(2)(CO)(8)] is obtained. In THF solution, at room temperature, reactions with phenylacetylene, styrene, and acetaldehyde give the derivatives of C-H activation [Re-2(mu-H)(mu-C drop CPh)(CO)(8)], [Re-2(mu-H)(mu-CH=C(H)Ph)(CO)(8)], and [Re-2(mu-H)(mu-eta(2)-C(Me)O)(CO)(8)]. Moreover, the activation of an sp(3) C-H bond in ethyl acetate occurs slowly when 3 is dissolved in the reactant itself, the resultant product being [Re-2(mu-H)(mu-eta(2)-CH2C(O)OEt)(CO)(8)].

  DOI：

  10.1021/om9806693
• 作为产物：
  描述：

  重氮甲烷 、 四氢呋喃 、 Re2(μ-H)2(CO)8 以 四氢呋喃 、 乙醚 为溶剂， 以30%的产率得到1,2-eq,eq-[Re2(THF)2(CO)8]
  参考文献：
  名称：

  1,2-eq,eq-[Re₂(CO)₈(THF)₂]:  A Reactive Re₂(CO)₈ Fragment That Easily Activates H−H and C−H Bonds

  摘要：

  The reaction of [Re-2(mu-H)(2)(CO)(8)] (1) with diazomethane at 193 K in THF-d(8) gives the unstable [Re-2(mu-H)(mu-CH3)(CO)(8)] derivative (2) containing a methyl group arising from the insertion of CH2 into a Re-H-Re bond. Isotopic perturbation of the equilibria by partial deuteration demonstrated that the methyl bridges the Re-Re bond in an unsymmetrical way, with a fast exchange between one agostic and two terminal C-H bonds. At temperatures higher than 253 K, 2 decomposes, in THF solution, with CH4 elimination to give the novel red complex 1,2-eq,eq-[Re-2(CO)(8)(THF)(2)] (3), which was characterized by NMR spectroscopy and X-ray analysis. In the solid form a staggered conformer of Ca symmetry was found. C-13 NMR analysis revealed the presence, in wet THF, of the aquo complexes [Re-2(CO)(8)(THF)(H2O)] (4) and [Re-2(CO)(8)(H2O)(2)] (5), whose formation is favored at low temperature (Delta H degrees for the formation of 5 from 4: -14.4(2) kJ mol(-1)). In solution, due to the lability of the THF ligands, 3 behaves as a "lightly stabilized" Re-2(CO)(8) fragment, capable of activating different E-H bonds. Reaction with HCl in THF leads to [Re-2(mu-H)(mu-Cl)(CO)(8)], while with H-2 the unsaturated starting material [Re-2(mu-H)(2)(CO)(8)] is obtained. In THF solution, at room temperature, reactions with phenylacetylene, styrene, and acetaldehyde give the derivatives of C-H activation [Re-2(mu-H)(mu-C drop CPh)(CO)(8)], [Re-2(mu-H)(mu-CH=C(H)Ph)(CO)(8)], and [Re-2(mu-H)(mu-eta(2)-C(Me)O)(CO)(8)]. Moreover, the activation of an sp(3) C-H bond in ethyl acetate occurs slowly when 3 is dissolved in the reactant itself, the resultant product being [Re-2(mu-H)(mu-eta(2)-CH2C(O)OEt)(CO)(8)].

  DOI：

  10.1021/om9806693

文献信息

• [Re6(μ-H)5(CO)24]−: The First Carbonyl Cluster with a Cyclohexane-Like Structure
  作者：Mirka Bergamo、Tiziana Beringhelli、Giuseppe D'Alfonso、Pierluigi Mercandelli、Massimo Moret、Angelo Sironi

  DOI：10.1002/(sici)1521-3773(19991203)38:23<3486::aid-anie3486>3.0.co;2-t

  日期：——
• [Re5(μ-H)4(CO)20]− and [Re5(μ-H)5(CO)20], Two Isolobal Analogues of Cyclopentane
  作者：Mirka Bergamo、Tiziana Beringhelli、Giuseppe D'Alfonso、Pierluigi Mercandelli、Massimo Moret、Angelo Sironi

  DOI：10.1002/(sici)1521-3773(19980817)37:15<2128::aid-anie2128>3.0.co;2-7

  日期：1998.8.17

  The first five-membered rings of metal atoms connected by M-M or M-H-M bonds only have been obtained by a Re2 +Re3 condensation in which a polyhydride acts as a bridging bidentate ligand toward a coordinatively unsaturated fragment (see scheme below). In spite of the octahedral coordination of the Re centers, the Re5 rings display conformations (twisted and envelope) comparable with those observed for organic five-membered rings of tetrahedral carbon atoms.