Mo₂Cp₂{(μ-C(Ph)CO)}(μ-PCy₂)(CO)₂ | 1208114-70-8

• 英文名称: Mo₂Cp₂{(μ-C(Ph)CO)}(μ-PCy₂)(CO)₂
• 英文别名: [Mo₂Cp₂{mu-C(Ph)CO}(mu-PCy₂)-(CO)₂]；[Mo2(η5-cyclopentadienyl)2(μ-phenylketenyl)(μ-dicyclohexylphosphide)(CO)2]；[Mo2(η5-C5H5)2(μ-C(Ph)CO)(μ-PCy2)(CO)2]
• CAS: 1208114-70-8
• 化学式: C₃₂H₃₇Mo₂O₃P
• 分子量: 692.498
• InChiKey: YNELOGBEENVOLP-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：

  Mo₂Cp₂{(μ-C(Ph)CO)}(μ-PCy₂)(CO)₂ 以 甲苯 为溶剂， 以83%的产率得到[Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(CO)2]
  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：

  一氧化碳 、 [Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(CO)2] 以 not given 为溶剂， 生成 Mo₂Cp₂{(μ-C(Ph)CO)}(μ-PCy₂)(CO)₂
  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

文献信息

• Carbyne–Carbyne Coupling and H-Shifts in Reactions of the Unsaturated Methoxy- and Hydroxycarbyne Complexes [Mo₂Cp₂(μ-COR)(μ-CPh)(μ-PCy₂)]⁺ with CO and Isocyanides
  作者：M. Angeles Alvarez、M. Esther García、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1021/acs.organomet.5b00166

  日期：2015.5.11

  analogously with CO (293 K, 4 bar) to give the hydroxyalkyne-bridged derivative [Mo2Cp2μ-η2:η2-C(OH)CPh}(μ-PCy2)(CO)2]BF4 (Mo–Mo = 2.6572(5) Å) as a result of C–C coupling between hydroxycarbyne and benzylidyne ligands, but this process could not be reversed photochemically. The latter complex could be prepared more efficiently via protonation of the ketenyl precursor [Mo2Cp2μ-C(Ph)CO}(μ-PCy2)(CO)2] with HBF4·OEt2

  所述不饱和methoxycarbyne络合物[沫2的CP 2（μ-COME）（μ-CPH）（μ-PCY 2）]（CF 3 SO 3）（CP =η 5 -C 5 H ^ 5 ;钼-钼= 2.4707（3 ）a）用CO（293 K，40巴）或CNR（233 K，R =反应吨卜，的Xyl），得到相应的methoxyalkyne桥接衍生物[沫2的CP 2 μ-η 2：η 2 -C（ OME）器CPh}（μ-PCY 2）L- 2 ]（CF 3 SO 3）是由甲氧基碳炔和苄炔配体之间的还原性C–C偶联（L = CO，CNR）引起的。在四氢呋喃溶液中光解后，二羰基产物的偶联反应可以完全逆转。相关hydroxycarbyne络合物[沫2的CP 2（μ-COH）（μ-CPH）（μ-PCY 2）] BF 4与CO（293 K，4巴）类似的反应，得到hydroxyalkyne桥接衍生物[沫2的CP 2 μ-η
• C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(CO)₂] with Small Unsaturated Organics
  作者：M. Esther García、Daniel García-Vivó、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1021/acs.organomet.6b00552

  日期：2016.10.24

  The ability of the title compound to promote C-C coupling processes has been analyzed by examining its reactions with diazoalkanes, alkynes, and other unsaturated organic molecules. The title compound reacted with N2CPh2 at room temperature to give a mixture of ketenyl complex [Mo2Cp2mu-kappa(1):eta(2)-C(Ph)CO}(mu-PCy2)(CO)(kappa(1)-N2CPh2)] and carbyne complex [Mo2Cp2(mu-CPh)(mu-PCy2)(CO)(kappa(1)-N2CPh2)], products which can be converted into each other by addition/removal of CO, respectively. In contrast, denitrogenation took place rapidly in analogous reactions with diazomethane and benzylazide at room temperature, to yield, respectively, the corresponding alkenyl [Mo2Cp2mu-kappa(1):eta(2)-C(Ph)CH2} (mu-PCy2) (CO)(2)] and iminoacyl [Mo2Cp2mu-C(Ph)NCH2Ph}(mu-PCy2)(CO)(2)] derivatives, following from selective C-C and C-N couplings. The title compound reacted at 333 K with methyl propiolate to give the corresponding propenylylidene derivative [Mo2Cp2mu-kappa(2):eta(3)-CPhCHC(CO2Me)}(mu-PCy2)(CO)(2)], as a result of selective coupling of the carbyne ligand to the terminal carbon of the alkyne. A related complex could be obtained when using the internal alkyne dimethyl acetylenedicarboxylate.
• Dehydrogenative Formation and Reactivity of the Unsaturated Benzylidyne-Bridged Complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(μ-CO)]: C−C and C−P Coupling Reactions
  作者：M. Angeles Alvarez、M. Esther García、M. Eugenia Martínez、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1021/om901053x

  日期：2010.2.22