| 167227-31-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 167227-31-8
• 化学式: C₅₀H₄₂O₄P₂Pd₂
• 分子量: 981.669
• InChiKey: CBGBZNRHTFZFIG-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：

  9-iodo-1,7-dicarba-closo-dodecaborane 、 以 氘代苯 为溶剂， 生成 iodophenylbis(triphenylphosphine)palladium 、 钯 、 1,7-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  Mechanistic Features of Boron−Iodine Bond Activation of B−Iodocarboranes

  摘要：

  Oxidative addition of the B-I bond of 9-iodo-m-carborane to [(Ph3P)(n)Pd] (n = 3, 4) is reversible, the equilibrium being shifted to the Pd(0) and the iodocarborane. In the presence of [(Ph3P)(4)Pd] and [Bu4N]Br in THF, 9-iodo-m-carborane undergoes halide exchange to produce 9-bromo-m-carborane. Coordinatively unsaturated Pd(0) and hydride Pd(II) species generated upon thermal decomposition of [(Ph3P)(2)Pa(Ph)(O2CH)] and [(Ph3P)(2)Pd-2(Ph)(2)(mu -O2CH)(2)] reduce 9-iodo-m-carborane to m-carborane with 100% selectivity. The thermal decomposition of [(Ph3P)(2)Pd-2(Ph)(2)(mu -O2CH)(2)] in the presence of excess 9-iodo-m-carborane and PhI (1:1) results in the formation of m-carborane (3%) and [(Ph3P)(2)Pd-2(Ph)(2)(mu -I)(2)] (97%), whose structure was confirmed by single-crystal X-ray diffraction. X-ray analysis of 9-iodo-m-carborane and m-carboran-9-yl(phenyl)iodonium tetrafluoroborate shows that in the iodonium salt the B-I bond is longer by ca. 0.03 Angstrom than in the iodocarborane. In contrast, the C-I bond distances in carboran-9-yl(phenyl)iodonium tetrafluoroborate (2.111(2) Angstrom) and in iodobenzene (2.098(4) Angstrom) are only marginally different. The elongation of the B-I bond, not the C-I bond, likely contribute s to (i) the enhanced reactivity of B-carboranyl(phenyl)iodonium cations toward nucleophiles and (ii) the remarkably high selectivity of these SN reactions that occur exclusively at the boron atom. A new crystallographic form of 9,10-diiodo-m-carborane is reported.

  DOI：

  10.1021/om0008575
• 作为产物：
  描述：

  甲酸 、 [(PPh3)2Pd2(Ph)2(μ-OH)2] 以 苯 为溶剂， 以91%的产率得到
  参考文献：
  名称：

  第一个可分离的有机钯甲酸酯配合物：合成，表征和X射线结构。配位不饱和钯（0）物种的便捷生成。

  摘要：

  [L(2)Pd(2)(R)(2)(mu-OH)(2)] complexes (L = PPh(3), R = Ph, Me) react with formic acid in benzene to give the first stable organopalladium formates, [L(2)Pd(2)(R)2(mu-HCOO)(2)] (1, R = Ph; 2, R = Me). Addition of L to 1 and 2 results in the formation of the less stable, but still isolable, [L(2)Pd(R)(HCOO)] (3, R = Ph; 4, R = Me). Complexes 1-4 have been characterized by elemental analysis and NMR and IR spectral data. The structure of 2 has been,confirmed by X-ray analysis of its 1:1.5 benzene solvate: monoclinic, space group P2(1)/n; a = 9.785(4) Angstrom, b = 24.909(8) Angstrom, c = 18.854(7) Angstrom, beta = 102.92(3)degrees; V = 4479(3) Angstrom, Z = 4; D-calcd = 1.441 g/cm(3); R = 0.044, R(w) = 0.066. The thermal decomposition of 4-4 in benzene or toluene at 30-55 degrees C gives CO2, RH, and highly reactive [L(n)Pd] (n = 1, 2). An exchange between the sigma-Me groups and phenyls of the PPh(3) ligand is observed in the course of the thermal decomposition of 2 in toluene at 55 degrees C. The thermolysis of 1 in the presence of PhI gives rise to [L(2)Pd(2)(Ph)(2)(mu-I)(2)] (5); likewise, the decomposition of 2 in the presence of Mel furnishes [L(2)Pd(2)(Me)(2)(mu-I)(2)] (6). However, when 1 is decomposed in the presence of Mel, both 5 and 6 are formed, with the ratio of 5 to 6 being higher at higher concentrations of MeI. A similar effect is observed when 2 is thermolyzed in the presence of PhI. This ''reverse'' selectivity leads to the recognition of two distinct mechanisms governing the Pd-catalyzed reductive dehalogenation of aryl halides with formate anion.

  DOI：

  10.1021/om00007a028