[Pd(1,3-bis(diisopropylphosphino)propane)]2(μ-1,3-bis(diisopropylphosphino)propane) | 148508-71-8

• 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(1,3-bis(diisopropylphosphino)propane)]2(μ-1,3-bis(diisopropylphosphino)propane)
• 英文别名: (1,3-bis(diisopropylphosphino)propane)3Pd2
• CAS: 148508-71-8
• 化学式: C₄₅H₁₀₂P₆Pd₂
• 分子量: 1041.99
• InChiKey: GRXUMDJGZBPDHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.92
• 重原子数：
  53.0
• 可旋转键数：
  18.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  (2-methylallyl)palladium-chloride dimer 、 1,3-二(二异丙基膦酰)丙烷 在 NaOH 作用下， 以 甲醇 、 甲苯 为溶剂， 以95%的产率得到[Pd(1,3-bis(diisopropylphosphino)propane)]2(μ-1,3-bis(diisopropylphosphino)propane)
  参考文献：
  名称：

  螯合剂对富电子钯配合物的结构和反应性的影响及其与催化作用的关系

  摘要：

  In order to clarify the origin of the ''chelate effect' in catalysis by palladium, complexes of (Pr2P(CH2)nPr2P)-Pr-i-Pr-i (n = 2, dippe; n = 3, dippp; n = 4, dippb), Ph2P(CH2)3PPh2 (dppp), and PiPr2 nBu were prepared and their structures, dynamic properties, and reactivities were compared. Pd(dippe)2 1d is a coordinatively saturated complex, both in solution and in the solid state. X-ray characterization exhibits a distorted tetrahedral geometry. The dippe bite angle is 87.05-degrees. The compound crystallizes in the orthorhombic space group Pnna with a = 16.713(3) angstrom, b = 17.561(3) angstrom, c = 11.116(2) angstrom, V = 3277(1) angstrom3, Z = 4. Pd(dippp)2 (1a) and Pd(dippb)2 (1e) are coordinatively unsaturated, trigonal complexes and are in equilibrium with the binuclear complexes LPd(eta2-L)PdL, 1b and 1f, respectively. Whereas 1d does not exhibit dynamic behavior, 1a and 1e undergo fast, intramolecular phosphine exchange, a process which is not observed with 1b and 1f. The trigonal complexes (dippp)PdPiPr2Bu (1c) and (PiPr2nBu)3Pd were also prepared for comparison. The dippp complexes 1a-1c react with aryl chlorides to produce cis-(dippp)Pd(C6H4X)Cl as the major product and trans-(eta1-dipp)2Pd(C6H4X)Cl as the minor one (X = 4-OMe, 4-Me, H, 3-OMe, 4-COMe, 4-CHO, 4-NO2). In contrast, the dippb complex 1e oxidatively adds chlorobenzene to yield only the trans complex (eta1-dippb)2Pd(Ph)Cl. Reaction monitoring reveals that the cis and trans complexes are formed in parallel pathways. Cis/trans equilibrium is on the cis side for dippp and on the trans side for dippb. Reactivity toward chlorobenzene follows the trend Pd(dippp)2 > Pd(PiPr2nBu)3 >> Pd(dippe)2 >> Pd(dPPP)2. These results are interpreted in terms of chelate stability, ligand basicity, concentration of the active 14e species and effect of the P-Pd-P angle on its reactivity. The dippp ligand is unique in that it is the only one of those studied which results in Pd(0) complexes which (a) exhibit high reactivity in oxidative addition and (b) form cis complexes preferentially.

  DOI：

  10.1021/om00029a025

文献信息

• Solution and Solid-State Structures of the Binuclear Zerovalent Palladium Complex [(dippe)Pd]₂(μ-dippe) (dippe = 1,2-Bis(diisopropylphosphino)ethane)
  作者：Michael D. Fryzuk、Guy K. B. Clentsmith、Steven J. Rettig、Gerhard Hägele

  DOI：10.1021/om950825v

  日期：1996.4.16

  The reaction of PdCl2(dippe), where dippe = 1,2-bis(diisopropylphosphino)ethane, with 2 equiv of KBEt(3)H in toluene generates the binuclear palladium(0) derivative [(dippe)Pd](2)(mu-dippe) (4) in 35% yield; alternatively, the reaction of [(eta(3)-C4H7)Pd](2)(mu-Cl)(2) with MeONa in the presence of 3 equiv of dippe generates 4 as well. Mechanistic studies on the attempted formation of mixed binuclear complexes are reported as well as the use of 4 as a catalyst for the reductive dechlorination of chloroarenes. Analysis of the second-order [AB(2)](2) spin system was accomplished by iteration of the 202.47 MHz P-31H-1} NMR spectrum of 4; the solution structure and the solid-state structures are found to be very nearly identical.