[Pd2(μ-Cl)2(COMe)2(SMe2)2] | 1049638-34-7

• 英文名称: [Pd2(μ-Cl)2(COMe)2(SMe2)2]
• 英文别名: [Pd₂(μ-Cl)₂(COMe)₂(SMe₂)₂]；[Pd(μ-Cl)(C(O)Me)(SMe2)]2
• CAS: 1049638-34-7
• 化学式: C₈H₁₈Cl₂O₂Pd₂S₂
• 分子量: 494.108
• InChiKey: WMLXJURKMGTYDK-UHFFFAOYSA-L

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：

  、 [Pd2(μ-Cl)2(COMe)2(SMe2)2] 以 氘代乙腈 为溶剂， 生成 trans-[Pd(μ-Cl)(COMe)(C(NEt2)Ph)]2
  参考文献：
  名称：

  Carbene and Carbonyl Transfer from [W(CO)₅(carbene)] to Palladium, Affording Palladium(II) Carbene Acyl Complexes

  摘要：

  The reaction of [W(CO)(5){C(NEt2)Ph}] (3) with [PdClR(SMe2)](2) (R = Me, Ph) occurs with transfer of carbene and carbonyl groups to give [PdCl{C(O)R)} {C(NEt2)Ph}](2) (R = Me, 4; R = Ph, 5). When the reaction is monitored for R = Me, only [PdCl(COMe)(SMe2)](2) and the final carbene 4 are observed, suggesting that the transfer and insertion of the carbonyl group are faster than the carbene transmetalation. Although CO insertion into M-X bonds is thermodynamically excluded in many systems (e.g., in M-halogen and M-C6F5 bonds), this study warns of the fact that CO is easily available when [M(CO)(5)(carbene)] complexes are used as carbene sources, whether for stoichiometric or for catalytic reactions. This CO could react with the intermediates or the products in these reactions.

  DOI：

  10.1021/om800358f
• 作为产物：
  描述：

  乙腈(五羰基)钨(0) 、 [Pd₂(μ-Cl)₂Me₂(SMe₂)₂] 以 not given 为溶剂， 生成 [Pd2(μ-Cl)2(COMe)2(SMe2)2]
  参考文献：
  名称：

  Carbene and Carbonyl Transfer from [W(CO)₅(carbene)] to Palladium, Affording Palladium(II) Carbene Acyl Complexes

  摘要：

  The reaction of [W(CO)(5){C(NEt2)Ph}] (3) with [PdClR(SMe2)](2) (R = Me, Ph) occurs with transfer of carbene and carbonyl groups to give [PdCl{C(O)R)} {C(NEt2)Ph}](2) (R = Me, 4; R = Ph, 5). When the reaction is monitored for R = Me, only [PdCl(COMe)(SMe2)](2) and the final carbene 4 are observed, suggesting that the transfer and insertion of the carbonyl group are faster than the carbene transmetalation. Although CO insertion into M-X bonds is thermodynamically excluded in many systems (e.g., in M-halogen and M-C6F5 bonds), this study warns of the fact that CO is easily available when [M(CO)(5)(carbene)] complexes are used as carbene sources, whether for stoichiometric or for catalytic reactions. This CO could react with the intermediates or the products in these reactions.

  DOI：

  10.1021/om800358f

文献信息

• Acyl–Carbene and Methyl–Carbene Coupling via Migratory Insertion in Palladium Complexes
  作者：Isabel Meana、Ana C. Albéniz、Pablo Espinet

  DOI：10.1021/om300462t

  日期：2012.8.13

  Pd–methyl group to give an alkyl palladium complex. The transfer of CO from tungsten, followed by insertion into the Pd–Me group, also occurs. This leads to the formation of a Pd–COMe group, which also undergoes migratory insertion of the carbene fragment. These results support that migratory insertion is a key C–C coupling step, as proposed for the new Pd-catalyzed transformations that use carbene precursors

  卡宾向钯-酰基键的迁移插入反应在单氨基卡宾和甲氧基卡宾中均已观察到。酰基衍生物[PdCl（COMe）C（NEt 2）Ph}（PPh 3）]经历酰基-卡宾偶联，生成烯醇盐型复合物[PdCl C（COMe）（NEt 2）Ph}（PPh 3）] 2（2）。该络合物通过还原消除而得到亚胺盐，或者通过烯醇盐的质子化而得到酮胺而分解。[Pd 2（μ-Cl）2（COMe）2（SMe 2）2 ]与[W（CO）5C（OMe）Ph}]导致未检测到的烯醇化钯，在质子化后通过与钯配位而稳定化[[PdCl 2 （OH）MeC═CPh（OMe}（SMe 2）]，8）。 [Pd 2（μ-Cl）2 Me 2（SMe 2）2 ]与[W（CO）5C（OMe）-Ph}]导致卡宾迁移进入Pd-甲基，从而得到烷基钯络合物。也发生了CO从钨的转移，然后插入Pd-Me组。这导致形成Pd–COMe基团，该基团也经历了卡宾片段的