trans-(PPh3)2PdI(C6H4I) | 71283-22-2

• 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-(PPh3)2PdI(C6H4I)
• 英文别名: trans-(PPh3)2Pd(I)(C6H4-4-I)；iodobenzene;palladium(2+);triphenylphosphane;iodide
• CAS: 71283-22-2
• 化学式: C₄₂H₃₄I₂P₂Pd
• 分子量: 960.908
• InChiKey: HTEWKBWRSYQNCU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.86
• 重原子数：
  47
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-(PPh3)2PdI(C6H4I) 以 苯 为溶剂， 以0%的产率得到
  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(三苯基膦)钯 、 1,4-二碘苯 以 甲苯 为溶剂， 以92%的产率得到trans-(PPh3)2PdI(C6H4I)
  参考文献：
  名称：

  线性均双金属钯配合物

  摘要：

  将C 6 H 4 -1,4-I 2（1）氧化添加到Pd（PPh 3）4（2）中得到单核反式-（Ph 3 P）2 Pd（C 6 H 4 -4-I）（ I）（3），其可以通过与[AgOTf]（4）反应而转化为反式-（Ph 3 P）2 Pd（C 6 H 4 -4-I）（OTf）（5）。复杂5可以在一系列的结构类型的独特阳离子单-和双核钯络合物的高产量可用于制备[反式- （PH 3 P）2的Pd（C 6 H ^ 4 -4-I）（L）] +（7，L ＝ C 4 H 4 N 2；9a，L ＝ C 5 H 4 N-4-CN；9b，L ＝ NC-4-C 5 H 4 N）和[反式-（C 6 H 4 -4 -I）（Ph 3 P）2 Pd← N∩N →Pd（PPh）3）2（C 6 H ^ 4 -4-I）] 2+（14A，N ∩ N = C 6 H ^ 4 -1,4-（CN）2 ; 14B，N ∩ N =（C 6

  DOI：

  10.1016/j.jorganchem.2006.05.034

文献信息

• A new approach to novel homobimetallic palladium complexes
  作者：D. Taher、B. Walfort、H. Lang

  DOI：10.1016/j.inoche.2004.05.023

  日期：2004.9

  Mononuclear trans-(PPh3)(2)Pd(I)(C6H4-4-I) (3), which is accessible by the oxidative addition of C6H4-1,4-I-2 (2) to (Ph3P)(4)Pd (1), reacts with [AgOTf] (4) in a 1:1 molar ratio to give trans-(PPh3)(2)Pd(C6H4-4-I)(OTf) (5). Complex 5 affords on treatment with 0.5 equivalents of 4,4'-dicyanobiphenyl (6) homobimetallic trans-[(PPh3)(2)(C6H4-4-I)Pd <-- Nequivalent toC-C6H4](2)(OTf)(2) (7). The latter species rearranges to give trans-[(PPh3)(2)(C6H4-4-PPh3)Pd <-- Nequivalent toC-C6H4](2)(OTf)(4) (8) and [(PPh3)(C6H4-4-PPh3)Pd(mu-I)](2)(OTf)(2) (9), respectively. A possible mechanism for the formation of 8 and 9 will be presented. The solid-state structure of 8 is reported. In 8 two [trans-(PPh3)(C6H4-4-PPh3)Pd](2+) fragments are bridged by the 4,4'-dicyanobiphenyl unit. (C) 2004 Elsevier B.V. All rights reserved.