[Pd(P(t)Bu2C(CH3)2CH2)(μ-Br)]2 | 207927-33-1

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: [Pd(P(t)Bu2C(CH3)2CH2)(μ-Br)]2
• 英文别名: ditert-butyl(2-methanidylpropan-2-yl)phosphane;palladium(2+);dibromide
• CAS: 207927-33-1；69721-11-5
• 化学式: C₂₄H₅₂Br₂P₂Pd₂
• 分子量: 775.272
• InChiKey: ZBQQBNSDBNNNKZ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  溴苯 、 二(三叔丁基膦)钯 以 甲苯 为溶剂， 生成 di-μ-bromobis(tri-t-butylphosphonino)dipalladium(I) 、 (tBu₃P)Pd(Ph)Br 、 (P(t)Bu3)2Pd(Ph)(Br) 、 [Pd(P(t)Bu2C(CH3)2CH2)(μ-Br)]2
  参考文献：
  名称：

  Autocatalytic Oxidative Addition of PhBr to Pd(P^tBu₃)₂ via Pd(P^tBu₃)₂(H)(Br)

  摘要：

  We report that Oxidative addition of bromobenzene to Pd ((PBu3)-Bu-t)(2) Occurs by an unusual autocatalytic mechanism. Studies on the effect of various additives showed that the degree of rate acceleration followed the trend: ((PBu3)-Bu-t)Pd (Ph)(Br) approximate to (Hp(t)Bu(3))Br < [((PBu3)-Bu-t)Pd(P-Br)](2) < ((PBu3)-Bu-t)(2)Pd (H)(Br). Studies on the reactions of Pd((PBu3)-Bu-t)(2) in the Presence of ((PBu3)-Bu-t)(2)Pd(H)(Br) showed that the concentration of ((PBu3)-Bu-t)(2)Pd(H)(Br) decreased only after the Pd(O) complex had been consumed. These data indicated that the catalyst in this Process is ((PBu3)-Bu-t)(2)Pd(H)(Br). Thermal decomposition of the three-coordinate Oxidative addition product ((PBu3)-Bu-t)(2)Pd(Ar)(Br) during the reaction of Pd((PBu3)-Bu-t)(2) and bromoarenes ultimately leads to formation Of ((PBu3)-Bu-t)(2)Pd(H)(Br). Parallel reactions of bromobenzene with ((PBu3)-Bu-t)(2)Pd(H)(Br) and Pd((PBu3)-Bu-t)(2) showed that the bromoarenes reacted considerably faster with the Pd(II) species than with the Pd(O) species. We therefore propose a catalytic cycle for oxidative addition in which PBu3t center dot HBr reacts with the Pd(O) species to form ((PBu3)-Bu-t)(2)Pd(H)(Br), and ((PBu3)-Bu-t)(2)Pd (H)(Br) reacts with the bromoarene, possibly though the anionic species [(HPBu3+)-Bu-t][((PBu3)-Bu-t)Pd(Br)(-)], to form [Pd((PBu3)-Bu-t)(Ar)(Br)].

  DOI：

  10.1021/ja711159y