[Mo3(η5-cyclopentadienyl)2(μ3-methylidyne)(μ-dicyclohexylphosphide)(CO)6(P(OMe)3)] | 1286281-97-7

• 英文名称: [Mo3(η5-cyclopentadienyl)2(μ3-methylidyne)(μ-dicyclohexylphosphide)(CO)6(P(OMe)3)]
• CAS: 1286281-97-7
• 化学式: C₃₂H₄₂Mo₃O₉P₂
• 分子量: 920.448
• InChiKey: XBYLPVYNYXJGNN-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：

  [Mo3(η5-cyclopentadienyl)2(μ3-methylidyne)(μ-dicyclohexylphosphide)(CO)6(P(OMe)3)] 以 甲苯 为溶剂， 以73%的产率得到[Mo2(η5-cyclopentadienyl)2(μ-methylidyne)(μ-dicyclohexylphosphide)(CO)]
  参考文献：
  名称：

  Binuclear Carbyne and Ketenyl Derivatives of the Alkyl-Bridged Complexes [Mo₂(η⁵-C₅H₅)₂(μ-CH₂R)(μ-PCy₂)(CO)₂] (R = H, Ph)

  摘要：

  The 30-electron benzylidyne complex [Mo2Cp2(mu-CPh)(mu-PCy2)(mu-CO)] (Cp = eta(5)-C5H5) could be conveniently prepared upon photolysis of the benzyl-bridged complex [Mo2Cp2(mu-CH2Ph)(mu-PCy2)(CO)(2)]. It reacted with CO to give the ketenyl complex [Mo2Cp2{mu-C(Ph)CO}(mu-PCy2)(CO)(2)] (2.6101(2) angstrom), which in turn could be selectively decarbonylated at 353 K to give the 32-electron benzylidyne derivative [Mo2Cp2(mu-CPh)(mu-PCy2)(CO)(2)] (Mo-Mo = 2.666(1) angstrom). Related methylidyne complexes could be obtained from the methyl-bridged complex [Mo2Cp2(mu-CH3)(mu-PCy2)(CO)(2)] via its trinuclear derivative [Mo3Cp2(mu(3)-CH)(mu-PCy2)(CO)(7)] Thus, the carbonylation of the latter cluster gave the ketenyl complex [Mo2Cp2{mu-C(H)CO}(mu-PCy2)(CO)(2)], whereas its reaction with P(OMe)(3) gave the substituted cluster [Mo3Cp2(mu(3)-CH)(mu-PCy2)(CO)(6){P(OMe)(3)}], which in turn could be thermally degraded to give selectively the 30-electron methylidyne derivative [Mo2Cp2(mu-CH)(mu-PCy2)(mu-CO)] (Mo-Mo = 2.467(1) angstrom). DFT calculations on the phenylketenyl complex revealed that the metal ligand interaction is intermediate between the extreme descriptions represented by the acylium (3-electron donor) and ketenyl (1-electron donor) canonical forms of this ligand.

  DOI：

  10.1021/om1011819
• 作为产物：
  描述：

  [Mo3(η5-cyclopentadienyl)2(μ3-methylidyne)(μ-dicyclohexylphosphide)(CO)7] 、 三甲氧基磷 以 甲苯 为溶剂， 以84%的产率得到[Mo3(η5-cyclopentadienyl)2(μ3-methylidyne)(μ-dicyclohexylphosphide)(CO)6(P(OMe)3)]
  参考文献：
  名称：

  Binuclear Carbyne and Ketenyl Derivatives of the Alkyl-Bridged Complexes [Mo₂(η⁵-C₅H₅)₂(μ-CH₂R)(μ-PCy₂)(CO)₂] (R = H, Ph)

  摘要：

  The 30-electron benzylidyne complex [Mo2Cp2(mu-CPh)(mu-PCy2)(mu-CO)] (Cp = eta(5)-C5H5) could be conveniently prepared upon photolysis of the benzyl-bridged complex [Mo2Cp2(mu-CH2Ph)(mu-PCy2)(CO)(2)]. It reacted with CO to give the ketenyl complex [Mo2Cp2{mu-C(Ph)CO}(mu-PCy2)(CO)(2)] (2.6101(2) angstrom), which in turn could be selectively decarbonylated at 353 K to give the 32-electron benzylidyne derivative [Mo2Cp2(mu-CPh)(mu-PCy2)(CO)(2)] (Mo-Mo = 2.666(1) angstrom). Related methylidyne complexes could be obtained from the methyl-bridged complex [Mo2Cp2(mu-CH3)(mu-PCy2)(CO)(2)] via its trinuclear derivative [Mo3Cp2(mu(3)-CH)(mu-PCy2)(CO)(7)] Thus, the carbonylation of the latter cluster gave the ketenyl complex [Mo2Cp2{mu-C(H)CO}(mu-PCy2)(CO)(2)], whereas its reaction with P(OMe)(3) gave the substituted cluster [Mo3Cp2(mu(3)-CH)(mu-PCy2)(CO)(6){P(OMe)(3)}], which in turn could be thermally degraded to give selectively the 30-electron methylidyne derivative [Mo2Cp2(mu-CH)(mu-PCy2)(mu-CO)] (Mo-Mo = 2.467(1) angstrom). DFT calculations on the phenylketenyl complex revealed that the metal ligand interaction is intermediate between the extreme descriptions represented by the acylium (3-electron donor) and ketenyl (1-electron donor) canonical forms of this ligand.

  DOI：

  10.1021/om1011819