Pd2{(η6-C6H5)Cr(CO)3}2(μ-Cl)2(PCy3)2 | 136805-07-7

• 英文名称: Pd2{(η6-C6H5)Cr(CO)3}2(μ-Cl)2(PCy3)2
• CAS: 136805-07-7
• 化学式: C₅₄H₇₆Cl₂Cr₂O₆P₂Pd₂
• 分子量: 1270.88
• InChiKey: ZIPAVXUOKATQRZ-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

• 作为反应物：
  描述：

  Pd2{(η6-C6H5)Cr(CO)3}2(μ-Cl)2(PCy3)2 在 CO 作用下， 以 苯 为溶剂， 以100%的产率得到Pd2{(η6-C6H5CO)Cr(CO)3}2(μ-Cl)2(PCy3)2
  参考文献：
  名称：

  在均相催化中的双金属活化。3.三羰基（氯苯）铬的甲氧基羰基化机理研究；可能的反应中间体的分离和反应

  摘要：

  The coordination of the Cr(CO)3 moiety to the aromatic ring allows the carbonylation of chlorobenzene, catalyzed by palladium complexes, to esters, aldehydes, amides or alpha-oxo-amides. The mechanism of methoxycarbonylation of tricarbonyl(chlorobenzene)chromium, (eta-6-C6H5Cl)Cr(CO)3, and the role of the Cr(CO)3 moiety are now investigated. Tricarbonyl(chlorobenzene)chromium reacts at room temperature with Pd(PPh3)4 or Pd(dba)2 and PR3 via an oxidative addition to give aryl-palladium complexes of the type {Pd[(eta-6-C6H5)Cr(CO)3](Cl)L(y)}2/y, which are monomers (L = PPh3 (1), PEt2Ph (4), PPh2Et (5)) or dimers (L = PPh3 (2), PCy3 (3)). By comparison, the oxidative addition of PhCl to Pd(PPh3)4 is known to proceed at 140-degrees-C, indicating that the coordination of Cr(CO)3 to PhCl greatly enhances the rate of this reaction. However, this reaction does not proceed with L2 = dppe or dpph, but the same complexes can be prepared by Cl-bridge cleavage and/or phosphine exchange with PR3 on Pd2[(eta-6-C6H5)Cr(CO)3]2(mu-Cl)2(PPh3)2 to give the monomers (L = PEt2Ph (4), PPh2Et (5); L2 = dppe (6), dpph (7)) and the dimer (L = PCy3 (3)). The X-ray structures of complexes trans-Pd2[(eta-6-C6H5)Cr(CO)3]2(mu-Cl)2(PCy3)2 (3) and cis-Pd[(eta-6-C6H5)Cr(CO)3]Cl (dppe) (6) have been detemined. Crystal data for 3: orthorhombic with the space group Pccm; a = 18.486 (8) angstrom, b = 20.401 (7) angstrom, c = 17.255 (6) angstrom, V = 6508 angstrom 3, Z = 8. Crystal data for 6: monoclinic with the space group P2(1)/n, a = 9.841 (2) angstrom, b = 12.783 (5) angstrom, c = 28.377 (2) angstrom, beta = 92.23 (1)-degrees, V = 3567 angstrom 3, Z = 4. These aryl-palladium complexes react at room temperature with CO under atmospheric pressure (L = PPh3, PEt2Ph; L2 = dpph) or 5 bar (L = PCy3) to give the corresponding monomeric or dimeric acyl-palladium complexes of the type {Pd[(eta-6-C6H5CO)Cr(CO)3](Cl)L(y)}2/y (y = 2: L = PPh3 (8), PEt2Ph (9), L2 = dpph (10); y = 1: L = PPh3 (11), PCy3 (12)). The reaction does not proceed with L2 = dppe even under 30 bar of CO; Cl-bridge cleavage and phosphine exchange with dppe on Pd2[(eta-6-C6H5CO)Cr(CO)3]2(mu-Cl)2(PPh3)2 enable the formation of cis-Pd[(eta-6-C6H5CO)Cr(CO)3]Cl(dppe) (13). Methanolysis of complexes Pd[(eta-6-C6H5CO)Cr(CO)3]Cl(PPh3)2 (8) and Pd2[(eta-6-C6H5CO)Cr(CO)3]2(mu-Cl)2(PPh3)2 (11) in the presence of triethylamine at room temperature proceeds rapidly and leads to the formation of (eta-6-C6H5COOMe)Cr(CO)3, which is the product of methoxycarbonylation of (eta-6-C6H5Cl)Cr(CO)3. Complexes {Pd[(eta-6-C6H5)Cr(CO)3]Cl(PPh3)y}2/y (1, 2) and {Pd[(eta-6-C6H5CO)Cr(CO)3]Cl(PPh3)y}2/y (8, 11) then appear to be reasonable intermediates in the catalytic cycle of methoxycarbonylation of (eta-6-C6H5Cl)Cr(CO)3. A possible mechanism for this reaction is discussed.

  DOI：

  10.1021/om00058a015
• 作为产物：
  描述：

  三环己基膦 、 tricarbonyl(η6-chlorobenzene)chromium 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 以 苯 为溶剂， 以63%的产率得到Pd2{(η6-C6H5)Cr(CO)3}2(μ-Cl)2(PCy3)2
  参考文献：
  名称：

  在均相催化中的双金属活化。3.三羰基（氯苯）铬的甲氧基羰基化机理研究；可能的反应中间体的分离和反应

  摘要：

  The coordination of the Cr(CO)3 moiety to the aromatic ring allows the carbonylation of chlorobenzene, catalyzed by palladium complexes, to esters, aldehydes, amides or alpha-oxo-amides. The mechanism of methoxycarbonylation of tricarbonyl(chlorobenzene)chromium, (eta-6-C6H5Cl)Cr(CO)3, and the role of the Cr(CO)3 moiety are now investigated. Tricarbonyl(chlorobenzene)chromium reacts at room temperature with Pd(PPh3)4 or Pd(dba)2 and PR3 via an oxidative addition to give aryl-palladium complexes of the type {Pd[(eta-6-C6H5)Cr(CO)3](Cl)L(y)}2/y, which are monomers (L = PPh3 (1), PEt2Ph (4), PPh2Et (5)) or dimers (L = PPh3 (2), PCy3 (3)). By comparison, the oxidative addition of PhCl to Pd(PPh3)4 is known to proceed at 140-degrees-C, indicating that the coordination of Cr(CO)3 to PhCl greatly enhances the rate of this reaction. However, this reaction does not proceed with L2 = dppe or dpph, but the same complexes can be prepared by Cl-bridge cleavage and/or phosphine exchange with PR3 on Pd2[(eta-6-C6H5)Cr(CO)3]2(mu-Cl)2(PPh3)2 to give the monomers (L = PEt2Ph (4), PPh2Et (5); L2 = dppe (6), dpph (7)) and the dimer (L = PCy3 (3)). The X-ray structures of complexes trans-Pd2[(eta-6-C6H5)Cr(CO)3]2(mu-Cl)2(PCy3)2 (3) and cis-Pd[(eta-6-C6H5)Cr(CO)3]Cl (dppe) (6) have been detemined. Crystal data for 3: orthorhombic with the space group Pccm; a = 18.486 (8) angstrom, b = 20.401 (7) angstrom, c = 17.255 (6) angstrom, V = 6508 angstrom 3, Z = 8. Crystal data for 6: monoclinic with the space group P2(1)/n, a = 9.841 (2) angstrom, b = 12.783 (5) angstrom, c = 28.377 (2) angstrom, beta = 92.23 (1)-degrees, V = 3567 angstrom 3, Z = 4. These aryl-palladium complexes react at room temperature with CO under atmospheric pressure (L = PPh3, PEt2Ph; L2 = dpph) or 5 bar (L = PCy3) to give the corresponding monomeric or dimeric acyl-palladium complexes of the type {Pd[(eta-6-C6H5CO)Cr(CO)3](Cl)L(y)}2/y (y = 2: L = PPh3 (8), PEt2Ph (9), L2 = dpph (10); y = 1: L = PPh3 (11), PCy3 (12)). The reaction does not proceed with L2 = dppe even under 30 bar of CO; Cl-bridge cleavage and phosphine exchange with dppe on Pd2[(eta-6-C6H5CO)Cr(CO)3]2(mu-Cl)2(PPh3)2 enable the formation of cis-Pd[(eta-6-C6H5CO)Cr(CO)3]Cl(dppe) (13). Methanolysis of complexes Pd[(eta-6-C6H5CO)Cr(CO)3]Cl(PPh3)2 (8) and Pd2[(eta-6-C6H5CO)Cr(CO)3]2(mu-Cl)2(PPh3)2 (11) in the presence of triethylamine at room temperature proceeds rapidly and leads to the formation of (eta-6-C6H5COOMe)Cr(CO)3, which is the product of methoxycarbonylation of (eta-6-C6H5Cl)Cr(CO)3. Complexes {Pd[(eta-6-C6H5)Cr(CO)3]Cl(PPh3)y}2/y (1, 2) and {Pd[(eta-6-C6H5CO)Cr(CO)3]Cl(PPh3)y}2/y (8, 11) then appear to be reasonable intermediates in the catalytic cycle of methoxycarbonylation of (eta-6-C6H5Cl)Cr(CO)3. A possible mechanism for this reaction is discussed.

  DOI：

  10.1021/om00058a015