[Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(μ-CO)] | 1208114-69-5

• 英文名称: [Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(μ-CO)]
• 英文别名: [Mo₂(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(μ-CO)]；Mo₂(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(μ-CO)；Mo₂Cp₂(μ-CPh)(μ-PCy₂)(μ-CO)；[Mo₂Cp₂(μ-CPh)(μ-PCy2)(μ-CO)]；[Mo2(η5-cyclopentadienyl)2(μ-benzylidyne)(μ-dicyclohexylphosphide)(CO)]
• CAS: 1208114-69-5
• 化学式: C₃₀H₃₇Mo₂OP
• 分子量: 636.477
• InChiKey: SNAFGDNTRGSAOL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(μ-CO)] 、 pentacarbonyl iron 以 甲苯 为溶剂， 反应 5.0h， 以89%的产率得到Mo₂Fe(η⁵-C₅H₅₎₂(μ₃-CPh)(μ-PCy₂)(CO)₅
  参考文献：
  名称：

  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)

  摘要：

  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.

  DOI：

  10.1016/j.jorganchem.2015.09.010
• 作为产物：
  描述：

  Mo₂Cp₂{(μ-C(Ph)CO)}(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

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
• 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
• Synthesis and DFT Study of a Diphenylsilanone-Bridged Dimolybdenum Complex
  作者：M. Angeles Alvarez、M. Esther García、Daniel García-Vivó、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1002/chem.201601598

  日期：2016.6.20

  Reaction of the 30‐electron benzylidyne complex [Mo2Cp2(μ‐CPh)(μ‐PCy2)(μ‐CO)] with excess Ph2SiH2 under visible‐UV irradiation yields the silylene‐bridged complex [Mo2Cp2(μ‐CPh)(μ‐PCy2)(μ‐SiPh2)]. This compound undergoes selective oxidation with O2 to give the unsaturated complex [Mo2Cp2(μ‐CPh)(μ‐PCy2)(μ‐κ1:κ1‐OSiPh2)], which contains an unprecedented bridging diphenylsilanone ligand, as confirmed

  30电子benzylidyne络合物[沫的反应2的CP 2（μ-CPH）（μ-PCY 2）（μ-CO）]用过量博士2的SiH 2可见紫外光照射下产生的亚甲硅基桥接的配合物[沫2的CP 2（μ-CPH）（μ-PCY 2）（μ-SIPH 2）]。该化合物经历与O-选择性氧化2，得到不饱和的复杂的[沫2的CP 2（μ-CPH）（μ-PCY 2）（μ-κ 1：κ 1 -OSiPh 2）]，其中包含前所未有的桥联二苯基硅酮配体，这一点已通过X射线衍射分析和DFT计算得到证实。根据相关的固态键长和理论计算，该配合物中心Mo 2 SiO环中的键接近于双金属硅环硅氧烷的极端描述。
• 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
• Reactions of the Carbyne-Bridged Radical Complex [Mo₂(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(μ-CO)]⁺with Bidentate Ligands Having E–H Bonds (E = O, S, N)
  作者：M. Angeles Alvarez、M. Esther García、Sonia Menéndez、Miguel A. Ruiz

  DOI：10.1021/om401192m

  日期：2014.3.10