[NBu4][(OsCl(η4-1,5-cyclooctadiene))2(μ-H)(μ-Cl)2] | 918299-38-4

• 英文名称: [NBu4][(OsCl(η4-1,5-cyclooctadiene))2(μ-H)(μ-Cl)2]
• 英文别名: [NBu4][(OsCl(η4-COD))2(μ-H)(μ-Cl)2]
• CAS: 918299-38-4
• 化学式: C₁₆H₂₅Cl₄Os₂*C₁₆H₃₆N
• 分子量: 982.055
• InChiKey: ABLWJGRGWCLWII-PKWKLEIRSA-J

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：

  lithium phenylacetylide 、 [NBu4][(OsCl(η4-1,5-cyclooctadiene))2(μ-H)(μ-Cl)2] 以 四氢呋喃 为溶剂， 以73%的产率得到[NBu4][(Os(phenylacetylido)(η4-1,5-cyclooctadiene))2(μ-H)(μ-Cl)2]
  参考文献：
  名称：

  Preparation and Characterization of Novel Os−Diolefin Dimers:  New Entry to Os−Cyclooctadiene Complexes

  摘要：

  The complex [H(EtOH)(2)][{OsCl(eta(4)-COD)}(2)(mu-H)(mu-Cl)(2)] (1) has been prepared in high yield by treatment of OsCl3 center dot 3H(2)O (54% Os) with 1,5-cyclooctadiene in ethanol under reflux. Under air, it is unstable and undergoes oxidation by action of O-2 to afford the neutral derivative {OsCl(eta(4)-COD)}(2)(mu-H)(mu-Cl)(2) (2). The terminal chlorine ligands of the anion of 1 are activated toward nucleophilic substitution. Thus, reaction of the salt [NBu4][{OsCl(eta(4)-COD)}(2)-( mu-H)(mu-Cl)(2)] (1a) with NaCp in toluene gives [NBu4][{Os(eta(1)-C5H5)(eta(4)-COD)}(mu-H)(mu-Cl)(2){OsCl(eta(4)-COD)}] (3) as a result of the replacement of one of the terminal chlorine atoms by the cyclopentadienyl ligand. The CH2 group of the latter can be deprotonated by the bridging methoxy ligand of the iridium dimer [Ir(mu-OMe)(eta(4)-COD)](2). The reaction leads to the trinuclear derivative [NBu4][{(eta(4)-COD)Ir(eta(5)-C5H4-eta(1))Os(eta(4)-COD)}(mu-H)(mu-Cl)(2){OsCl(eta(4)-COD)}] (4) containing a bridging C5H4 ligand that is eta(1)-coordinated to an osmium atom of the dimeric unit and eta(5)-coordinated to the Ir(eta(4)-COD) moiety. Salt 1a also reacts with LiC=CPh. In this case, the reaction produces the substitution of both terminal chlorine ligands to afford the bis(alkynyl) derivative [NBu4][{Os(C equivalent to CPh)(eta(4)-COD)}(2)(mu-H)(mu-Cl)(2)] (5). Complexes 1, 2, 3, and 4 have been characterized by X-ray diffraction analysis. Although the separations between the osmium atoms are short, between 2.6696(4) and 2.8633(5) angstrom, theoretical calculations indicate that only in 2 is there direct metal-metal interaction, as the bond order is 0.5.

  DOI：

  10.1021/ic0612799
• 作为产物：
  描述：

  [H(ethanol)2][(OsCl(η4-1,5-cyclooctadiene))2(μ-H)(μ-Cl)2] 、 tert-butylammonium hexafluorophosphate(V) 以 乙醇 为溶剂， 以75%的产率得到[NBu4][(OsCl(η4-1,5-cyclooctadiene))2(μ-H)(μ-Cl)2]
  参考文献：
  名称：

  Preparation and Characterization of Novel Os−Diolefin Dimers:  New Entry to Os−Cyclooctadiene Complexes

  摘要：

  The complex [H(EtOH)(2)][{OsCl(eta(4)-COD)}(2)(mu-H)(mu-Cl)(2)] (1) has been prepared in high yield by treatment of OsCl3 center dot 3H(2)O (54% Os) with 1,5-cyclooctadiene in ethanol under reflux. Under air, it is unstable and undergoes oxidation by action of O-2 to afford the neutral derivative {OsCl(eta(4)-COD)}(2)(mu-H)(mu-Cl)(2) (2). The terminal chlorine ligands of the anion of 1 are activated toward nucleophilic substitution. Thus, reaction of the salt [NBu4][{OsCl(eta(4)-COD)}(2)-( mu-H)(mu-Cl)(2)] (1a) with NaCp in toluene gives [NBu4][{Os(eta(1)-C5H5)(eta(4)-COD)}(mu-H)(mu-Cl)(2){OsCl(eta(4)-COD)}] (3) as a result of the replacement of one of the terminal chlorine atoms by the cyclopentadienyl ligand. The CH2 group of the latter can be deprotonated by the bridging methoxy ligand of the iridium dimer [Ir(mu-OMe)(eta(4)-COD)](2). The reaction leads to the trinuclear derivative [NBu4][{(eta(4)-COD)Ir(eta(5)-C5H4-eta(1))Os(eta(4)-COD)}(mu-H)(mu-Cl)(2){OsCl(eta(4)-COD)}] (4) containing a bridging C5H4 ligand that is eta(1)-coordinated to an osmium atom of the dimeric unit and eta(5)-coordinated to the Ir(eta(4)-COD) moiety. Salt 1a also reacts with LiC=CPh. In this case, the reaction produces the substitution of both terminal chlorine ligands to afford the bis(alkynyl) derivative [NBu4][{Os(C equivalent to CPh)(eta(4)-COD)}(2)(mu-H)(mu-Cl)(2)] (5). Complexes 1, 2, 3, and 4 have been characterized by X-ray diffraction analysis. Although the separations between the osmium atoms are short, between 2.6696(4) and 2.8633(5) angstrom, theoretical calculations indicate that only in 2 is there direct metal-metal interaction, as the bond order is 0.5.

  DOI：

  10.1021/ic0612799