(1,2-bis(diisopropylphosphino)ethane)2Pd | 148508-73-0

• 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: (1,2-bis(diisopropylphosphino)ethane)2Pd
• 英文别名: [Pd(1,2-bis(diisopropylphosphino)ethane)₂]；[Pd(dippe)₂]；(dippe)2Pd；[(dippe)2Pd]；2-di(propan-2-yl)phosphanylethyl-di(propan-2-yl)phosphane;palladium
• CAS: 148508-73-0
• 化学式: C₂₈H₆₄P₄Pd
• 分子量: 631.131
• InChiKey: XBYTVXIKOXSWAD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.17
• 重原子数：
  33.0
• 可旋转键数：
  8.0
• 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

• 作为反应物：
  描述：

  (1,2-bis(diisopropylphosphino)ethane)2Pd 、 1-chloro-3-(diisopropylphosphino)propane 以 N,N-二甲基甲酰胺 为溶剂， 生成
  参考文献：
  名称：

  通过磷化氢辅助脂肪族CCl键的氧化加成形成P，C螯合的钯配合物

  摘要：

  已经给出了（氯烷基）膦1-氯-3-（二异丙基膦基）丙烷（3）与螯合的Pd（0）配合物的反应，导致了P，C-螯合的配合物。甲基-π-烯丙基氯化钯二聚物与1，3-（二异丙基膦基）丙烷和碱的反应得到双核络合物2a。Pd（dippe）2（dippe = 1,2-双（二异丙基膦基）乙烷）与3反应生成单核双螯合配合物6。如所期望的，脂族C 3 Cl键在分子中向金属中心的分子内配位氧化加成比正丁基氯的分子间反应的快得多。2a的X射线结构 被确定。

  DOI：

  10.1016/0022-328x(95)05544-y
• 作为产物：
  描述：

  [(1,2-(bis-di-isopropylphosphino)ethane)PdCl2] 在 sodium triethylborohydride 作用下， 以 四氢呋喃 、 氘代苯 、 甲苯 为溶剂， 80.0 ℃ 、101.33 kPa 条件下， 反应 12.0h， 生成 (1,2-bis(diisopropylphosphino)ethane)2Pd
  参考文献：
  名称：

  室温下由反应性（浸渍）Pd片段激活的碳-硫键活化

  摘要：

  [Pd（dippe）（μ-H）] 2（1）和[（μ-dippe）Pd] 2（2）（dippe = 1,2-双（二异丙基膦基）乙烷）对C–S键的反应性对噻吩衍生物和硫醚进行了研究，从而得到了CS键活化产物。通过1 H，31 P和13 C NMR光谱，元素分析和X射线衍射对源自噻吩底物的噻吩四环进行了全面表征。的C-S插入产品的稳定性通过进行随后的热力学稳定性顺序（dippe）竞争实验的Pd（κ探测2 Ç，小号苯并噻）（6）>（dippe）的Pd（κ 2 ç，小号-dibenzothiophene）（8）>（dippe）的Pd（κ 2 ç，小号-噻吩）（3）。研究了噻菌四环与小分子（例如H 2，CO和炔烃）的反应性。

  DOI：

  10.1021/acs.organomet.5b00194

文献信息

• The synthesis and structural properties of [M(dippe)(η2-C4H4S)] complexes of Pd and Pt and comparison with their Ni analog
  作者：Tülay A. Ateşin、Stephen S. Oster、Karlyn Skugrud、William D. Jones

  DOI：10.1016/j.ica.2005.10.052

  日期：2006.6

  X-ray structural and NMR spectroscopic data for the ring-opened thiophene complexes [Pd(dippe)(T)] (2), and [Pt(dippe)(T)] (3) are now presented. The complex [Ni(dippe)(T)] (1), where T = (eta(2)-C,S-C4H4S), was reported by our group, previously. The structural and bonding properties of complexes 2 and 3 were compared with those of complex 1. DFT calculations were carried out to rationalize their relative stabilities and structural properties. Compound 1 loses thiophene at ambient temperature in solution, while compound 2 decomposes rapidly in both acetone-d(6) and THF-d(8) with k(obs) = 7.15(9) x 10(-5) and 7.7(3) x 10(-5) s(-1), respectively, to give products that varied by solvent. Complex 3 does not lose thiophene at temperatures below 100 degrees C. The Delta G(0) values determined from DFT calculations are consistent with the observed stabilities of the complexes. The single crystal X-ray structures of all three complexes contain a disordered thienyl fragment in the asymmetric unit due to the interchange of the position of sulfur in the metal-inserted thiophenic ring. The thiophenic moiety is relatively flat in 1, 2 and 3, which is attributed to the open ligand environment at the M(dippe) fragment. All three complexes possess square-planar geometry around the metal center and have bond-length alternation among the thiophenic carbons, which indicates double bond localization. The calculated bond lengths are in good agreement with experimental data. Molecular orbital (MO) and natural bonding orbital (NBO) analyses were carried out to rationalize the results. (c) 2005 Elsevier B.V. All rights reserved.
• Chelate effect on the structure and reactivity of electron-rich palladium complexes and its relevance to catalysis
  作者：Moshe Portnoy、David Milstein

  DOI：10.1021/om00029a025

  日期：1993.5

  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.
• Mechanistic Insights in the Exchange of Arylthiolate Groups in Aryl(arylthiolato)palladium Complexes Supported by a Dippe Ligand
  作者：Lloyd Munjanja、William W. Brennessel、William D. Jones

  DOI：10.1021/acs.organomet.5b00662

  日期：2015.9.28

  Carbon sulfur activation of phenyl p-tolyl sulfide by a mixture of [Pd(dippe)(mu-H)](2) (1a) and dinudear Pd(0), [(mu-dippe)Pd](2) (1b) (dippe = 1,2-bis(diisopropylphosphino)-ethane), to yield four carbon sulfur activation products, (dippe)Pd(p-tolyl)(SPh) (3a), (dippe)Pd(Ph)(S-p-tolyl) (3b), (dippe)Pd(SPh)(Ph)(3c), and (dippe)Pd(p-toly1)(S-p-tolyl) (3d), was investigated. The carbon sulfur complexes 3a-3d were completely characterized by H-1, P-31, and C-13 NMR spectroscopy, elemental analysis, and X-ray diffraction. Exchange interactions between arylthiolate groups in (dippe)Pd(Ar)-(SAr') (3a-3d) were investigated, leading to understanding the mechanism of interconversions among the complexes.
• Room-Temperature Carbon–Sulfur Bond Activation by a Reactive (dippe)Pd Fragment
  作者：Lloyd Munjanja、William W. Brennessel、William D. Jones

  DOI：10.1021/acs.organomet.5b00194

  日期：2015.5.11

  The reactivity of [Pd(dippe)(μ-H)]2 (1) and [(μ-dippe)Pd]2 (2) (dippe = 1,2-bis(diisopropylphosphino)ethane) toward C–S bonds in thiophene derivatives and thioethers was investigated, which led to C–S bond activation products. The thiapalladacycles derived from thiophenic substrates were fully characterized by 1H, 31P, and 13C NMR spectroscopy, elemental analysis, and X-ray diffraction. The stability

  [Pd（dippe）（μ-H）] 2（1）和[（μ-dippe）Pd] 2（2）（dippe = 1,2-双（二异丙基膦基）乙烷）对C–S键的反应性对噻吩衍生物和硫醚进行了研究，从而得到了CS键活化产物。通过1 H，31 P和13 C NMR光谱，元素分析和X射线衍射对源自噻吩底物的噻吩四环进行了全面表征。的C-S插入产品的稳定性通过进行随后的热力学稳定性顺序（dippe）竞争实验的Pd（κ探测2 Ç，小号苯并噻）（6）>（dippe）的Pd（κ 2 ç，小号-dibenzothiophene）（8）>（dippe）的Pd（κ 2 ç，小号-噻吩）（3）。研究了噻菌四环与小分子（例如H 2，CO和炔烃）的反应性。
• Formation of P,C-chelated palladium complexes by phosphine-assisted oxidative addition of an aliphatic CCl bond
  作者：Portnoy Moshe、Yehoshua Ben-David、David Milstein

  DOI：10.1016/0022-328x(95)05544-y

  日期：1995.11

  ylphosphino)propane (3) with chelated Pd(0) complexes have been given, leading to P,C-chelated complexes. Reaction of a methyl-π-allypalladium chloride dimer with 1,3-(diisopropylphosphino)propane and a base gives the binuclear complex 2a. Pd(dippe)2 (dippe = 1,2-bis(diisopropylphosphino)ethane) reacts with 3 to yield the mononuclear bis-chelated complex 6. As expected, the intramolecular coordinatively

  已经给出了（氯烷基）膦1-氯-3-（二异丙基膦基）丙烷（3）与螯合的Pd（0）配合物的反应，导致了P，C-螯合的配合物。甲基-π-烯丙基氯化钯二聚物与1，3-（二异丙基膦基）丙烷和碱的反应得到双核络合物2a。Pd（dippe）2（dippe = 1,2-双（二异丙基膦基）乙烷）与3反应生成单核双螯合配合物6。如所期望的，脂族C 3 Cl键在分子中向金属中心的分子内配位氧化加成比正丁基氯的分子间反应的快得多。2a的X射线结构 被确定。