(1,3-bis(diisopropylphosphino)propane)PdI2 | 155142-76-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: (1,3-bis(diisopropylphosphino)propane)PdI2
• 英文别名: [PdI2(di(i-propylphosphino)propane)]；[(dippp)PdI2]
• CAS: 155142-76-0
• 化学式: C₁₅H₃₄I₂P₂Pd
• 分子量: 636.611
• InChiKey: RAXYHGMUOFRVCM-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.74
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• 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

• 作为反应物：
  描述：

  (1,3-bis(diisopropylphosphino)propane)PdI2 以 甲苯 为溶剂， 生成 {(1,3-bis(diisopropylphosphino)propane)palladium}(η2-dimethyl acetylenedicarboxylate)
  参考文献：
  名称：

  Binuclear Palladium Complexes with Bridging Hydrides. Unusual Coordination Behavior of LiBEt4 and NaBEt4

  摘要：

  The reaction of Pd(dippp)Cl-2 (dippp = 1,3-bis(diisopropylphosphino)propane) with a 1:1 mixture of LiBEt(2)H(2) and LiBEt(4) in THF generates the binuclear hydride derivative [(dippp)Pd](2)(mu-H)(2).LiBEt(4) (1) in which the LiBEt(4) is bound to the palladium hydride core. The bare palladium hydride dimer [(dippp)Pd](2)(mu-H)(2) (2) was prepared by reaction of 2 equiv of KBEt(3)H in toluene with Pd(dippp)I-2. Addition of LiBEt(4) to the bare palladium dimer 2 generates the LiBEt(4) adduct 1; this approach has been extended to the preparation of [(dippp)Pd](2)(mu-H)2.NaBEt(4) (3) and [(dippp)Pd](2)(mu-H)(2).LiAlEt(4) (4) by the addition of NaBEt(4) and LiAlEt(4) respectively to 2. On the basis of NMR spectroscopy, there is no evidence for dissociation of the lithium of sodium berate or aluminate salts from the hydride dimer but the ME'Et(4) (M = Li, Na; E' = B, Al) units are labile on the basis of exchange studies and variable temperature NMR data. Crystals of [(dippp)Pd](2)(mu-H)(2).LiBEt(4)0.5(C6H14) (1) are monoclinic, a = 11.537(2) Angstrom, b = 19.114(2) Angstrom, c = 24.020(1) Angstrom, beta = 98.674(9)degrees, Z = 4, space group P2(1)/n; those of [(dippp)Pd](2)(mu-H)(2) (2) are monoclinic, a = 13.128(1) Angstrom, b = 14.362(4) Angstrom, c = 20.353(1) Angstrom, beta = 99.593(6)degrees, Z = 4, space group P2(1)/n; and those of [(dippp)-Pd](2)(mu-H)(2).NaBEt(4) (3) are monoclinic, a = 20.099(2) Angstrom, b = 11.457(5) Angstrom, c = 21.600(3) Angstrom, beta = 92.87(1)degrees, Z = 4, space group P2(1)/c. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.033, 0.052, and 0.033 (R(W) = 0.029, 0.054, and 0.028) for 5954, 4560, and 5018 reflections with I greater than or equal to 3 sigma(I), respectively. In the solid-state structure of 1, there are three C-H...Li interactions from the ethyl groups attached to boron whereas in the solid-state structure of 3 there are four such C-H...Na interactions.

  DOI：

  10.1021/ja00088a017
• 作为产物：
  描述：

  1,3-二(二异丙基膦酰)丙烷 以 丙酮 为溶剂， 生成 (1,3-bis(diisopropylphosphino)propane)PdI2
  参考文献：
  名称：

  Binuclear Palladium Complexes with Bridging Hydrides. Unusual Coordination Behavior of LiBEt4 and NaBEt4

  摘要：

  The reaction of Pd(dippp)Cl-2 (dippp = 1,3-bis(diisopropylphosphino)propane) with a 1:1 mixture of LiBEt(2)H(2) and LiBEt(4) in THF generates the binuclear hydride derivative [(dippp)Pd](2)(mu-H)(2).LiBEt(4) (1) in which the LiBEt(4) is bound to the palladium hydride core. The bare palladium hydride dimer [(dippp)Pd](2)(mu-H)(2) (2) was prepared by reaction of 2 equiv of KBEt(3)H in toluene with Pd(dippp)I-2. Addition of LiBEt(4) to the bare palladium dimer 2 generates the LiBEt(4) adduct 1; this approach has been extended to the preparation of [(dippp)Pd](2)(mu-H)2.NaBEt(4) (3) and [(dippp)Pd](2)(mu-H)(2).LiAlEt(4) (4) by the addition of NaBEt(4) and LiAlEt(4) respectively to 2. On the basis of NMR spectroscopy, there is no evidence for dissociation of the lithium of sodium berate or aluminate salts from the hydride dimer but the ME'Et(4) (M = Li, Na; E' = B, Al) units are labile on the basis of exchange studies and variable temperature NMR data. Crystals of [(dippp)Pd](2)(mu-H)(2).LiBEt(4)0.5(C6H14) (1) are monoclinic, a = 11.537(2) Angstrom, b = 19.114(2) Angstrom, c = 24.020(1) Angstrom, beta = 98.674(9)degrees, Z = 4, space group P2(1)/n; those of [(dippp)Pd](2)(mu-H)(2) (2) are monoclinic, a = 13.128(1) Angstrom, b = 14.362(4) Angstrom, c = 20.353(1) Angstrom, beta = 99.593(6)degrees, Z = 4, space group P2(1)/n; and those of [(dippp)-Pd](2)(mu-H)(2).NaBEt(4) (3) are monoclinic, a = 20.099(2) Angstrom, b = 11.457(5) Angstrom, c = 21.600(3) Angstrom, beta = 92.87(1)degrees, Z = 4, space group P2(1)/c. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.033, 0.052, and 0.033 (R(W) = 0.029, 0.054, and 0.028) for 5954, 4560, and 5018 reflections with I greater than or equal to 3 sigma(I), respectively. In the solid-state structure of 1, there are three C-H...Li interactions from the ethyl groups attached to boron whereas in the solid-state structure of 3 there are four such C-H...Na interactions.

  DOI：

  10.1021/ja00088a017

文献信息

• Reactivity of electrophilic palladium alkyl cations stabilized by electron-rich chelating diphosphine ligands. Evidence for dinuclear intermediates and the formation of a dinuclear mixed-valence methyl cation ‡
  作者：Michael D. Fryzuk、Guy K. B. Clentsmith、Steven J. Rettig

  DOI：10.1039/a800152i

  日期：——

  is the dinuclear mixed-valence species [Pd(dippe)(µ-CO)Pd(dippe)Me][BAr4], which is accompanied by the formation of acetone (Me2CO) and the dicarbonyl dication [Pd(dippe)(CO)2]2+. Presumably, methyl transfer occurs at some stage from the methyl cation to generate the methyl–acetyl complex, Pd(dippe)Me(COMe); reductive elimination of acetone under CO from the methyl–acetyl complex produces the Pd0 complex

  富电子-钯烷基阳离子，[钯（dippe）R]的反应性+ BAR 4 -（dippe = 1,2-双（二异丙基）乙烷; R =η 3 -CH 2 PH或CH 3 ; BAR 4  =报道了具有各种小分子的B [3,5-（F 3 C）2 C 6 H 3 ] 4 }）。尽管苄基阳离子对一氧化碳和二氢没有反应性，但相应的甲基阳离子[Pd（dippe）Me（s）] +（s = Et 2 O，THF或邻二氯苯）与H 2迅速反应生成二氢桥联的二聚体[（dippe）Pd] 2（µ-H）2 } 2+，并与CO生成二核价的阳离子络合物[Pd（dippe）（µ-CO）Pd（ dippe）Me] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr 4 ]。另外，甲基阳离子可以从中性二烷基络合物中提取烷基；因此，在Pd（dippe）（CH 2 Ph）2中添加[Pd（dippe）Me（s）] +会导致形成甲基苄基衍生物Pd（dippe）Me（CH 2 P
• Synthesis of the Elusive (R₃P)₂MF₂ (M = Pd, Pt) Complexes
  作者：Anette Yahav、Israel Goldberg、Arkadi Vigalok

  DOI：10.1021/ja0377753

  日期：2003.11.1

  previously unknown palladium(II) and platinum(II) difluoro phosphine complexes are described. These complexes can be obtained either via a halide metathesis reaction with AgF in dichloromethane or by reacting the corresponding dimethyl complexes with XeF2. While the Pt(II) complexes can be prepared with both aryl- and alkyl-phosphine ligands, the stability of the Pd(II) complexes is limited to those

  描述了以前未知的钯 (II) 和铂 (II) 二氟膦配合物的合成和表征。这些配合物可以通过卤化物与 AgF 在二氯甲烷中的复分解反应或通过相应的二甲基配合物与 XeF2 反应获得。虽然 Pt(II) 配合物可以用芳基和烷基膦配体制备，但 Pd(II) 配合物的稳定性仅限于那些具有顺式取向的三烷基膦配体。
• Fryzuk, Michael D.; Lloyd, Brian R.; Clentsmith, Guy K. B., Journal of the American Chemical Society, 1991, vol. 113, p. 4332 - 4334
  作者：Fryzuk, Michael D.、Lloyd, Brian R.、Clentsmith, Guy K. B.、Rettig, Steven J.

  DOI：——

  日期：——