[η(5)-1-(diphenylphosphino)-2,4-diphenylcyclopentadienyl]tricarbonylmolybdenum iodide | 184951-23-3

• 英文名称: [η(5)-1-(diphenylphosphino)-2,4-diphenylcyclopentadienyl]tricarbonylmolybdenum iodide
• 英文别名: (η(5)-1-Ph2P-2,4-Ph2C5H2)(CO)3MoI；[(η5-(1-Ph2P-2,4-Ph2)C5H2)(CO)3MoI]
• CAS: 184951-23-3
• 化学式: C₃₂H₂₂IMoO₃P
• 分子量: 708.343
• InChiKey: AMDFTWIVKNROJY-UHFFFAOYSA-M

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：

  tris(dibenzylideneacetone)dipalladium (0) 、 [η(5)-1-(diphenylphosphino)-2,4-diphenylcyclopentadienyl]tricarbonylmolybdenum iodide 以 not given 为溶剂， 生成
  参考文献：
  名称：

  金属催化交叉偶联反应领域的新前沿。钯促进金属-碳键的形成。有机金属合成新工具的范围和机理

  摘要：

  摘要 介绍了 Pd 催化的金属-碳键形成过程的合成用途和反应机理的研究。M–CC–R 型（M=Fe、Ru、Mo、W；R=H、烷基、Ph）的简单 σ-金属金属乙炔化物、M–CC–Thiop 型均质和异质双金属配合物的制备–CC–M′ (Thiop=2,5-噻吩; M, M′=Fe, Ru, Mo, W)，M型聚金属乙炔化物系链–CC–Thiop–CC–M′(η 5 -Cp)–CC–Thiop–CC–(η 5 -Cp)M′–CC–Thiop–CC–M (M=Re, Mn; M′=Fe), 金属乙炔化物报道了[–M–CC–Ar–CC–] n 型聚合物（Ar=2,5-噻吩，1,4-亚苯基）。通过使用适当设计的模型底物，参与催化循环的主要中间体（即氧化加成、金属转移）已被分离和充分表征。反应机理的动力学和光谱研究证明，根据反应条件，金属转移步骤可通过两种途径进行：(i) 在氧化加成络合物

  DOI：

  10.1016/s0022-328x(02)01274-3
• 作为产物：
  描述：

  tris(acetonitrile)tricarbonylmolybdenum(0) 、 1,2-二碘乙烷 、 (η(5)-2,4-Ph2C5H3)Tl 、 二苯基氯化膦 在 BuLi 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以98%的产率得到[η(5)-1-(diphenylphosphino)-2,4-diphenylcyclopentadienyl]tricarbonylmolybdenum iodide
  参考文献：
  名称：

  钯催化金属碳键形成的机理。氧化加成和过渡金属中间体的分离†

  摘要：

  为了研究Pd催化的金属-碳键形成的反应机理，模型化合物[η 5 -1-PH 2 P-2,4-PH 2 ç 5 ħ 2 ]（CO）3 MI（M =钼，12 ; M = W，13）已经制备并且在偶联条件下研究了它们的反应。的治疗12和13与化学计量量零价钯的产生的复合物[η 5 -1-PH 2 P-2,4-PH 2 ç 5 ħ 2 ]（CO）3 MPD（PPH 3）I（M =钼，16; M = W，17）通过在Pd 0上氧化添加M-1部分。中间体的后续反应16和17与4-硝基-1- [2-（三丁基锡烷基）乙炔基]苯（卜3的SnO⋮Ç（C 6 H ^ 4）p -NO 2，18）通向转移金属化产物的形成[η 5 -1-PH 2 P-2,4-PH 2 ç 5 ħ 2 ]（CO）3 MPD（PPH 3）C⋮ç（C 6 H ^ 4）p -NO 2（M = Mo，19 ; W，20），已对其进行了分离和表

  DOI：

  10.1021/om9601965

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.
• Full Picture of the Catalytic Cycle Underlying Palladium-Catalyzed Metal−Carbon Bond Formation
  作者：Simona Tollis、Valentina Narducci、Paola Cianfriglia、Claudio Lo Sterzo、Egidio Viola

  DOI：10.1021/om980167p

  日期：1998.6.1

  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.