[Mo3(η5-cyclopentadienyl)2(μ3-methylidyne)(μ-dicyclohexylphosphide)(CO)7] | 1021839-18-8

• 英文名称: [Mo3(η5-cyclopentadienyl)2(μ3-methylidyne)(μ-dicyclohexylphosphide)(CO)7]
• 英文别名: [Mo3(η5-cyclopentadienyl)2(μ3-CH)(μ-dicyclohexylphosphide)(CO)7]；[Mo3(η5-C5H5)2(μ3-CH)(μ-PCy2)(CO)7]；[Mo3Cp2(μ3-CH)(μ-PCy2)(CO)7]
• CAS: 1021839-18-8
• 化学式: C₃₀H₃₃Mo₃O₇P
• 分子量: 824.382
• InChiKey: KWCLADDMMHJXRK-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)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
• 作为产物：
  描述：

  [Mo2(η5-cyclopentadienyl)2(μ-CH3)(μ-dicyclohexylphosphide)(CO)2] 、 molybdenum hexacarbonyl 以 甲苯 为溶剂， 以80%的产率得到[Mo3(η5-cyclopentadienyl)2(μ3-methylidyne)(μ-dicyclohexylphosphide)(CO)7]
  参考文献：
  名称：

  的异金属衍生物的不饱和甲基桥联配合物[沫2（η 5 -C 5 H ^ 5）2（μ-CH 3）（μ-PCY 2）（CO）2 ]。亚甲基桥连簇的光化学生成

  摘要：

  所述的光化学反应甲基桥连的络合物[沫2的Cp 2（μ-CH 3）（μ-PCY 2）（CO）2 ]（1）（CP =η 5 -C 5 H ^ 5）与羰基配合物[ M（CO）6 ]（M =铬，钼，W）和[MnCp'（CO）3 ]（CP'=η 5 -C 5 H ^ 4 CH 3）得到相应的电子精确次甲基桥连的衍生物[MMO 2的Cp 2（μ 3 -CH）（μ-PCY 2）（CO）7]（钼-钼= 2.9340（13）一种用于M = W）和[MnMo 2的Cp 2 CP'（μ 3 -CH）（μ-PCY 2）（CO）4 ]（钼-钼= 2.9678（6） Å），产量高。在类似条件下，反应1用的[Ru 3（CO）12 ]给出46电子次甲基-桥连的簇[沫2 RuCp 2（μ 3 -CH）（μ-PCY 2）（CO）5 ]（钼-Mo = 2.6824（7）a）中，用甲氧基-桥连的类似物少量沿着[沫2 RuCp 2（μ

  DOI：

  10.1021/om900961u

文献信息

• Reactivity of the α-Agostic Methyl Bridge in the Unsaturated Complex [Mo₂(η⁵-C₅H₅)₂(μ-η¹:η²-CH₃)(μ-PCy₂)(CO)₂]: Migratory Behavior and Methylidyne Derivatives
  作者：M. Angeles Alvarez、Daniel García-Vivó、M. Esther García、M. Eugenia Martínez、Alberto Ramos、Miguel A. Ruiz

  DOI：10.1021/om800061z

  日期：2008.5.1

  The bridging methyl ligand present in the title compound can migrate up to the cyclopentadienyl (Cp) site upon reaction with CO to achieve an overall exchange between the methyl and hydrogen (Cp) positions. In the presence of different metal-carbonyl complexes, easy dehydrogenation of the methyl group takes place under photochemical conditions to give methylidyne-bridged heterometallic clusters.