[PdI(Ph)(tri-tert-butylphosphine)] | 457949-31-4

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [PdI(Ph)(tri-tert-butylphosphine)]
• 英文别名: [PdI(P(tert-butyl)3)(phenyl)]；[PdI(phenyl)(P(tert-butyl)3)]；PhPd(t-Bu3P)I
• CAS: 457949-31-4；636583-99-8
• 化学式: C₁₈H₃₂IPPd
• 分子量: 512.75
• InChiKey: XHFPWFKGBNOHOO-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：

  [PdI(Ph)(tri-tert-butylphosphine)] 、 C13取代的一氧化碳 以 氘代氯仿 为溶剂， 反应 0.13h， 生成
  参考文献：
  名称：

  Efficient ¹¹C-Carbonylation of Isolated Aryl Palladium Complexes for PET: Application to Challenging Radiopharmaceutical Synthesis

  摘要：

  We describe the successful implementation of palladium-aryl oxidative addition complexes as stoichiometric reagents in carbonylation reactions with (CO)-C-11 to produce structurally challenging, pharmaceutically relevant compounds. This method enables the first C-11-carbonyl labeling of an approved PET tracer, [C-11]raclopride, for the dopamine D2/D3 receptor by carbonylation with excellent radiochemical purity and yield. Two other molecules, [C-11]olaparib and [C-11]JNJ 31020028, were efficiently labeled in this manner. The technique distinguishes itself from existing methods by the markedly improved purity profiles of the tracer molecules produced and provides access to complex structures in synthetically useful yields, hereby offering a viable alternative to other C-11-labeling strategies.

  DOI：

  10.1021/ja511441u
• 作为产物：
  描述：

  溴苯 、 二(三叔丁基膦)钯 以 氯苯 为溶剂， 以50%的产率得到[PdI(Ph)(tri-tert-butylphosphine)]
  参考文献：
  名称：

  Barrios-Landeros, Fabiola; Carrow, Brad P.; Hartwig, John F., Journal of the American Chemical Society, 2009, vol. 131, p. 8141 - 8154

  摘要：

  DOI：

文献信息

• Synthesis, Structure, Theoretical Studies, and Ligand Exchange Reactions of Monomeric, T-Shaped Arylpalladium(II) Halide Complexes with an Additional, Weak Agostic Interaction
  作者：James P. Stambuli、Christopher D. Incarvito、Michael Bühl、John F. Hartwig

  DOI：10.1021/ja037928m

  日期：2004.2.1

  The oxidative addition of phenyl bromide and iodide to Pd(Q-phos)2 was faster than oxidative addition to Pd(1-AdPtBu2)2 or Pd(PtBu3)2. Several of the arylpalladium complexes were characterized by X-ray diffraction. All of the arylpalladium(II) complexes are T-shaped monomers. The phenyl ligand, which has the largest trans influence, is located trans to the open coordination site. The complexes appear

  已经制备了一系列含有单个膦配体的单体芳基钯 (II) 配合物 LPd(Ph)X（L = 1-AdPtBu2、PtBu3 或 Ph5FcPtBu2（Q-phos）；X = Br、I、OTf）。在 1 当量膦存在下，将芳基溴或芳基碘氧化加成到体积庞大的三烷基膦的双连接钯 (0) 配合物或 Pd(dba)2（dba = 二亚苄基丙酮），生成相应的芳基钯 (II) 配合物收益良好。相比之下，苯氯氧化加成到双连接钯 (0) 配合物不会产生芳基钯 (II) 配合物。苯基三氟甲磺酸酯氧化加成到 PdL2（L = 1-AdPtBu2、PtBu3 或 Q-phos）也没有形成芳基钯 (II) 配合物。三氟甲磺酸银与 (1-AdPtBu2)Pd(Ph)Br 反应以良好的收率提供相应的芳基钯 (II) 三氟甲磺酸盐。苯基溴化物和碘化物氧化加成到 Pd(Q-phos)2 比氧化加成到 Pd(1-AdPtBu2)2
• Synthesis, Characterization, and Reactivity of Monomeric, Arylpalladium Halide Complexes with a Hindered Phosphine as the Only Dative Ligand
  作者：James P. Stambuli、Michael Bühl、John F. Hartwig

  DOI：10.1021/ja0264394

  日期：2002.8.1

  indicated only weak M-H-C interactions. Addition of 2-adamantyl-di-tert-butyl phosphine to 1 led to ligand exchange and formation of 2-adamantyl-di-tert-butyl phosphine complex 2. Addition of P(t-Bu)(3) generated free aryl bromide and Pd[P(t-Bu)(3)](2). Reactivity of complex 1 with nucleophiles provided evidence of the intermediacy of these complexes in palladium-catalyzed cross-coupling reactions. Complex

  我们报告了几种含有三叔丁基膦、1-金刚烷基二叔丁基膦或 2-金刚烷基二叔丁基膦的单体芳基钯 (II) 卤化物配合物的分离和结构表征。X 射线衍射、IR 光谱和理论研究表明复合物可能通过激动相互作用而稳定。例如，在 1-金刚烷基-苯基溴化钯配合物 1 的 X 射线结构中，从最近的氢原子到钯金属中心的距离为 2.26(3) A。计算的 Pd-H 距离为 2.28 A，谐波振动频率与测量距离一致，但 Wiberg 键指数仅表明 MHC 相互作用较弱。将 2-金刚烷基-二叔丁基膦加成 1 导致配体交换并形成 2-金刚烷基-二叔丁基膦配合物 2。添加 P(t-Bu)(3) 生成游离芳基溴和 Pd[P(t-Bu)(3)](2)。配合物 1 与亲核试剂的反应性提供了这些配合物在钯催化的交叉偶联反应中的中介作用的证据。配合物1与胺和碱反应形成相应的芳胺，与叔丁醇反应形成相应的醚，与硼酸和氟化物反应形成相应
• Directly Observed Reductive Elimination of Aryl Halides from Monomeric Arylpalladium(II) Halide Complexes
  作者：Amy H. Roy、John F. Hartwig

  DOI：10.1021/ja037959h

  日期：2003.11.1

  with five haloarenes. Reductive elimination of aryl chloride was most favored thermodynamically, and elimination of aryl iodide was the least favored. However, reductive elimination from the aryl chloride complex was the slowest, and reductive elimination from the aryl bromide complex was the fastest. These data show that the electronic properties of the halide, not the thermodynamic driving force for

  单体的三配位芳基钯 (II) 卤化物络合物经过芳基卤化物的还原消除，形成游离的卤代芳烃和 Pd(0)。将 P(t-Bu)3 添加到 Pd[P(t-Bu)3](Ar)(X) (X = Cl, Br, I) 后，观察到芳基氯化物、溴化物和碘化物的还原消除。用五种卤代芳烃建立了观察还原消除和氧化加成之间平衡的条件。在热力学上最有利于芳基氯的还原消除，而最不利于芳基碘的消除。然而，芳基氯络合物的还原消除最慢，芳基溴络合物的还原消除最快。这些数据表明卤化物的电子特性，而不是消除反应加成的热力学驱动力，控制卤代芳烃的添加和消除速率。机理数据表明，芳基溴化物可逆还原消除形成 Pd[P(t-Bu)3] 和游离芳基溴化物，随后 P(t-Bu)3 限速配位形成 Pd[P(t-Bu) )3]2。