[Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(CO)2] | 1286281-95-5

• 英文名称: [Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(CO)2]
• 英文别名: [Mo2(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(CO)₂]；Mo₂(η⁵-C₅H₅₎₂(μ-CPh)(μ-PCy₂)(CO)₂；Mo₂Cp₂(μ-CPh)(μ-PCy₂)(CO)₂；[Mo₂Cp₂(mu-CPh)(mu-PCy₂)(CO)₂]；[Mo2(η5-cyclopentadienyl)2(μ-benzylidyne)(μ-dicyclohexylphosphide)(CO)2]；[Mo2(C5H5)2(μ-benzylidyne)(μ-PCy2)(CO)2]
• CAS: 1286281-95-5
• 化学式: C₃₁H₃₇Mo₂O₂P
• 分子量: 664.487
• InChiKey: QLNCFMCOVDNIIX-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：

  [Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(CO)2] 以 甲苯 为溶剂， 生成 [Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(μ-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：

  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

文献信息

• Electronic Structure and Reactivity of the Carbyne-Bridged Dimolybdenum Radical [Mo₂(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(μ-CO)]⁺
  作者：M. Angeles Alvarez、M. Esther García、Daniel García-Vivó、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1021/om300989j

  日期：2013.1.14

  the 30-electron nitrosyl complex [Mo2Cp2(μ-CPh)(μ-PCy2)(μ-NO)]BF4. Deprotonation of cis-[Mo2Cp2(μ-η1:η3-CHPh)(O)(μ-PCy2)(CO)]BF4 gives the neutral carbyne complex cis-[Mo2Cp2(μ-CPh)(O)(μ-PCy2)(CO)] (Mo–Mo = 2.8024(5) Å), which upon protonation reverts to its carbene precursor, via the corresponding hydroxo complex. Related trans isomers can be prepared through protonation reactions of trans-[Mo2Cp

  所述不饱和化合物[沫2的CP 2（μ-CPH）（μ-PCY 2）（μ-CO）]（1，CP =η 5 -C 5 H ^ 5）反应以在存在痕量的水[FeCP 2 ] BF 4，得到hydroxycarbyne络合物[沫的混合物2的CP 2（μ-COH）（μ-CPH）（μ-PCY 2）] BF 4（次要）和羟配合物〔沫2的CP 2（μ -CPh）（OH）（μ-PCY 2）（CO）] BF 4（主要产物），后者迅速重新排列，得到异构体卡宾顺- [沫2的CP 2（μ-η 1：η 3 -CHPh）（O）（μ-PCY 2）（CO）] BF 4（MO-沫= 2.9435（3））。类似的反应发生用苯酚，得到选择性地将相关phenoxo络合物[沫2的CP 2（μ-CPH）（OPH）（μ-PCY 2）（CO）] BF 4。相反，在[FeCP 2 ] BF 4存在下1与H 2 SiPh 2或H 3 BNH 2 t
• Chalcogenoacyl-bridged derivatives of the unsaturated carbyne complex [Mo 2 ( η 5 -C 5 H 5 ) 2 ( μ -CPh)( μ -PCy 2 )(CO) 2 ]
  作者：M. Ángeles Alvarez、M. Esther García、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1016/j.jorganchem.2016.11.019

  日期：2017.1

  visible-UV light, but instead rearranged into the corresponding cis-dicarbonyl isomers cis-[Mo2Cp2μ-η2:η2-C(Ph)E}(μ-PCy2)(CO)2] (Mo−Mo = 2.9208(5) Å, C−S = 1.745(5) Å in the thioacyl complex), in a process where no reaction intermediates were detected. The coordination of the chalcogenoacyl ligand in the cis-dicarbonyl isomers is analogous to that observed in the corresponding trans isomers, and involves

  32电子苄基桥联络合物[Mo 2 CP 2（μ- CPh）（μ- PCy 2）（CO）2 ]与元素硫族元素E n（E = S，Se）在333 K下反应，得到相应的衍生物反式- [沫2的CP 2 μ - η 2：η 2 -C（PH）电子}（μ -PCy 2）（CO）2 ]，从另外一个硫属原子的给沫以下2中心的C面钼2母体化合物中的PC核，从而形成桥接硫属酰基配体的5电子供体（硫酰基复合物中的Mo-Mo = 2.8662（5）Å，CS = 1.757（5））。这些热稳定的产品不与可见光的UV光辐照下脱羰进行，而是重新排列到对应的顺式二羰基的异构体的顺式- [沫2的CP 2 μ - η 2：η 2 -C（PH）电子}（μ -PCy 2）（CO）2 ]（在硫酰基复合物中，Mo-Mo = 2.9208（5）Å，CS = 1.745（5）Å），在此过程中未检测到任何反应中间体。硫代酰基配体的配
• Heterometallic clusters derived from the unsaturated carbyne-bridged dimolybdenum complexes [Mo 2 (η 5 -C 5 H 5 ) 2 (μ-CPh) (μ-PCy 2 ) (CO) x ] (x = 1, 2)
  作者：M. Angeles Alvarez、M. Esther García、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1016/j.jorganchem.2015.09.010

  日期：2015.12

  The carbonyl-bridged complex [Mo2Cp2(mu-CPh) (mu-FCY2) (mu-CO)] (1) reacted with [Fe-2(CO)91 at room temperature to give the 46-electron trinuclear cluster [FeMo2Cp2(mu(3)-CPh) (11-PCy2) (CO)(5)] (Mo Mo = 2.6782(4) A), and a similar Mo2Ru cluster was obtained upon reaction with [Ru-3(CO)(12) under irradiation with visible-UV light (Cp = 115-05H5). Compound 1 reacted with [Co-2(CO)(8) at room temperature to give the 60-electron tetrahedral cluster [Co2MO2CP2(13-CFh) (mu-PCY2) (CO)(7)], which in solution exits as an equilibrium mixture of two isomers and presumably displays phosphide and carbyne ligands in a cisoid arrangement. This compound evolved thermally to give a third isomer having these ligands arranged in a transoid way (P-Mo-C = 126.3(1)degrees, Mo-Mo = 2.9612(6) angstrom). The dicarbonyl complex [Mo2Cp2(11-CPh) (11-PCY2) (CO)(21) (2) reacted with W(C0)6 under visible-UV light irradiation to give two thermally unstable isomers of the 46-electron trinuclear cluster [Mo2WCP2(113-CFh) (P-PCY2) (C0)61. Reaction of 2 with [AuCl(PR3)] (R = Me, p-tol, 'Pr) in the presence of TIPF6 gave first the corresponding cationic clusters trans-[AuMo2Cp2(m-CPh) (11.-PCy2) (CO)(2)(PR3)1PF(6), which then evolved thermally to the more stable isomers cis-[AuMo2CP2(13-CPh) (11.-PCy2) (CO)(2)(PR3)(1)PF6 (Mo Mo = 2.810(1) A for R = 'Pr), selectively formed with a syn conformation of the carbyne and Cp ligands, except for the PMe3 complex. In contrast, reaction of 2 with CuCI led to a cluster of composition [CuMO2CICp2(m-CPh) (11-PCY2) (CO)(21), presumably present as a monomer in solution, but certainly appearing in the solid state as a centrosymmetric dimer held by bridging Cu CI Cu interactions (Mo Mo = 2.8004(5), Cu Cl = 2.309(1), 2.409(1) angstrom). (C) 2015 Elsevier BY. All rights reserved.
• 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.
• Multisite Reactivity of the Central Mo₂CP Core in the Unsaturated Carbyne-Bridged Complex [Mo₂(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(CO)₂]
  作者：M. Angeles Alvarez、M. Esther García、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1021/om2003738

  日期：2011.7.25