trans-PdMe(I)(PMePh2)2 | 42582-53-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-PdMe(I)(PMePh2)2
• CAS: 42582-53-6
• 化学式: C₂₇H₂₉IP₂Pd
• 分子量: 648.799
• InChiKey: NGZSWONSULXKQV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.97
• 重原子数：
  31.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  trans-iodomethylbis(triphenylphosphine)palladium(II) 、 trans-PdMe(I)(PMePh2)2 以 氘代苯 为溶剂， 生成 (methyldiphenyl-l5-phosphaneyl)(methylene)(triphenyl-l5-phosphaneyl)palladium(V) iodide
  参考文献：
  名称：

  Methyl/Phenyl Exchange between Palladium and a Phosphine Ligand. Consequences for Catalytic Coupling Reactions

  摘要：

  The methyl ligand of trans-CH3Pd(PPh(3))(2)I (1) exchanges with a phenyl from its PPh(3) ligand, initially giving PhPd(PPh(3))(PMePh(2))I (4). The PMePh(2) ligand of 4 then exchanges with a PPh(3) of 1 to give CH3Pd(PPh(3))(PMePh(2))I and with the PMePh(2) ligand of more 4 to give PhPd(PPh(3))(2)I and trans-PhPd(PMePh(2))(2)I. The observed rate constant for the disappearance of 1 is about 7 x 10(-5) s(-1) at 75 degrees C. The rearrangement is irreversible, does not involve a free phosphonium cation, and does not require phosphine dissociation. The rearrangement competes with transmetalation when 1 is treated with tin reagents, leading to coupling products incorporating phenyls from PPh(3). Relatively electropositive phosphine substituents seem reluctant to rearrange onto palladium.

  DOI：

  10.1021/ja00138a012
• 作为产物：
  描述：

  四(甲基苯基膦)钯 在 碘甲烷 作用下， 以 苯 为溶剂， 以88%的产率得到trans-PdMe(I)(PMePh2)2
  参考文献：
  名称：

  钯的 1,1-还原消除机制

  摘要：

  顺式异构体的消除是分子内的，这由缺乏与全氘甲基钯类似物的交叉确定，并显示出一级动力学（k = 1.04 x 10/sup -3/s/sup -1/，L = PPh/sub 3/ , 60/sup 0/C; K = (6.5 to 9.5) X 10/sup -5/s/sup -1/, L = PPh/sub 2/CH/sub 3/, 60/sup 0/C; k = 4.78 x 10/sup -7/s/sup -1/, L/sub 2/ = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/, 80/sup 0/C) . 反应混合物中二苯基乙炔的存在将钯(0)产物捕获为双(二苯基甲基膦)(二苯基乙炔)钯络合物。尽管 (TRANSPHOS) 二甲基钯不会经历乙烷的 1,1-还原消除，但在 25/sup 0/C 下向该复合物的 Me/sub 2/SO 溶液中添加更多 »

  DOI：

  10.1021/ja00535a018

文献信息

• DOUBLE CARBONYLATION REACTIONS OF METHYL- AND PHENYLPALLADIUM(II) COMPLEXES IN THE PRESENCE OF SECONDARY AMINES AFFORDING α-KETO AMIDES
  作者：Fumiyuki Ozawa、Akio Yamamoto

  DOI：10.1246/cl.1982.865

  日期：1982.6.5

  The reactions of trans-PdR(X)(PMePh2)2 (R = Me, X = I and R = Ph, X = Br) with carbon monoxide in the presence of secondary amines, R’2NH, were found to give α-keto amides, RCOCONR’2, as double carbonylation products under mild conditions in good yields and selectivities.

  发现反式 PdR(X)(PMePh2)2（R = Me，X = I 和 R = Ph，X = Br）与一氧化碳在仲胺 R'2NH 存在下的反应得到 α-酮酰胺，RCCOCONR'2，作为双羰基化产物在温和条件下以良好的产率和选择性。
• Ozawa, Fumiyuki; Sugimoto, Takeshi; Yuasa, Yasuhiro, Organometallics, 1984, vol. 3, # 5, p. 683 - 692
  作者：Ozawa, Fumiyuki、Sugimoto, Takeshi、Yuasa, Yasuhiro、Santra, Manoranjan、Yamamoto, Takakazu、Yamamoto, Akio

  DOI：——

  日期：——
• Mechanisms of 1,1-reductive elimination from palladium: elimination of ethane from dimethylpalladium(II) and trimethylpalladium(IV)
  作者：A. Moravskiy、J. K. Stille

  DOI：10.1021/ja00404a034

  日期：1981.7