[η(5)-1-(diphenylphosphino)-2,4-diphenylcyclopentadienyl]tricarbonylmolybdenum(C*CPh) | 207725-37-9

• 英文名称: [η(5)-1-(diphenylphosphino)-2,4-diphenylcyclopentadienyl]tricarbonylmolybdenum(C*CPh)
• 英文别名: [(η5-(1-Ph2P-2,4-Ph2)C5H2)(CO)3Mo(CCPh)]
• CAS: 207725-37-9
• 化学式: C₄₀H₂₇MoO₃P
• 分子量: 682.566
• InChiKey: JONLKCFEQBWXGP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  [η(5)-1-(diphenylphosphino)-2,4-diphenylcyclopentadienyl]tricarbonylmolybdenum-Pd(PPh3)(C*CPh) 在 1,2-双(二苯基膦)乙烷 作用下， 以 N,N-二甲基甲酰胺-d7 为溶剂， 生成 双(1,2-双(二苯基膦)乙烷)钯 、 [η(5)-1-(diphenylphosphino)-2,4-diphenylcyclopentadienyl]tricarbonylmolybdenum(C*CPh)
  参考文献：
  名称：

  Full Picture of the Catalytic Cycle Underlying Palladium-Catalyzed Metal−Carbon Bond Formation

  摘要：

  A catalytic cycle of reaction between [eta(5)-1-(diphenylphosphino) -2,4-diphenylcyclopentadienyl]tricarbonylmetal iodides, [eta(5)-1-Ph2P-2,4-Ph2C5H2]M(CO)(3)I (1a, M = Mo; 1b, M = W), with zerovalent palladium and tributyltin acetylides affords the final acetylide products [eta(5)-1-Ph2P-2,4-Ph2C5H2]M(CO)(3)C=CPh (5a, M = Mo; 5b, M = W). This communication describes the main processes and intermediates involved in this palladium-catalyzed metal-carbon bond formation.

  DOI：

  10.1021/om980167p

文献信息

• Synthesis and Characterization of Trimetallic Complexes Containing M−Pd−M Arrays (M = Mo, W) and Their Relevance in Palladium-Catalyzed Metal−Carbon Bond Formation
  作者：Francesco Angelucci、Antonella Ricci、Claudio Lo Sterzo、Dante Masi、Claudio Bianchini、Gabriele Bocelli

  DOI：10.1021/om020043j

  日期：2002.7.1

  The heterobimetallic complexes [MPd(PPh3)(Cequivalent toC-Ph)(CO)(3)(eta(5)-C-5-C5H2Ph2(PPh2)] (5a, M = Mo; 5b, M = W) convert under chromatography to diastereomeric mixtures of the new trimetallic clusters [PdM(CO)(3)(eta(5)-C5H2Ph2(PPh2)}(2)] (M = Mo, 9a; W, 9b), which contain a linear M-Pd-M array clamped between two (diphenyl)cyclopentadienyl-diphenylphosphino ligands. Diastereomeric pure forms of both trimetallic clusters 9a,b were obtained by fractional crystallization procedures, and the molecular structures of rac-9a and rac-9b were determined by single-crystal X-ray diffraction analyses. The trimetallic complexes 9a,b have been found to be intermediates in coupling reactions between M-I moieties and Bu(3)SnCequivalent toC-Ph, to form metallacetylides M-Cequivalent toC-Ph. Independent high-yield synthetic routes to 9a,b have been developed.
• Mechanism of the Palladium-Catalyzed Metal−Carbon Bond Formation. A Dual Pathway for the Transmetalation Step
  作者：Antonella Ricci、Francesco Angelucci、Mauro Bassetti、Claudio Lo Sterzo

  DOI：10.1021/ja011644p

  日期：2002.2.1

  The mechanism of the transmetalation step in the metal-carbon bond-formation process catalyzed by palladium complexes has been studied by spectroscopic and kinetic methods. The reaction of properly designed model complexes [eta(5)-(1-Ph2P-2,4-Ph-2)C5H2](CO)(3)MoPd(PR3)] (3, R = Ph; 15, R = Bu; 16, R = Me), resulting from oxidative addition of a Mo-I moiety to a palladium center, with aryltributyltinacetylicles Bu3Sn-C=C-(p-XC6H4) (11a, X = H; 11b, X = Cl) yields the products of transmetalation [eta(5)-(1-Ph-2- P-2,4-Ph-2)C5H2](CO)(3)MoPd(PR3)-C=C-(p-XC6H4) (5a,b). The reaction, which shows a strong dependence on the nature of the phosphine ligand PR3 (Ph > Bu > Me) and less so on the nature of the p-substituent X group, proceeds through two competing pathways, depending on the initial concentration of substrate. At high [3] (congruent to10(-2) M), the transmetalation proceeds through an intermediate species (12) formed by the interaction of complex 3 with 11 a. This associative complex accumulates in the presence of added PPh3 and has been characterized spectroscopically. At low [3] (congruent to10(-4) M), the reaction rate shows an inverse dependence on the concentration of the complex. This is due to the formation of a solvent-coordinate species (13), in which PPh3 has been substituted by a dimethylformamide (DMF) molecule, as shown by UV-vis and P-31 NMR spectroscopy. Values of k(obs) depend on the concentration and nature of the aryltributyltinacetylides, in agreement with the existence of a kinetically detectable intermediate. A dimeric iodide bridged complex [eta(5)-(1-Ph2P-2,4-Ph-2)C5H2}(CO)(3)MoPdl](2) (14) has been obtained during attempts at isolating 13, which changes quantitatively into 13 upon dissolution in DMF and reacts with 11a to give the transmetalation product.