[(1,2-(bis-di-isopropylphosphino)ethane)PdCl2] | 96165-43-4

• 英文名称: [(1,2-(bis-di-isopropylphosphino)ethane)PdCl2]
• 英文别名: [(1,2-bis(diisopropylphosphino)ethane)PdCl₂]；[(dippe)PdCl₂]
• CAS: 96165-43-4
• 化学式: C₁₄H₃₂Cl₂P₂Pd
• 分子量: 439.682
• InChiKey: OYDXORQIGDHPPP-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：

  [(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
• 作为产物：
  描述：

  二(氰基苯)二氯化钯 、 1,2-双(二-异丙基膦基)乙烷 以 丙酮 为溶剂， 生成 [(1,2-(bis-di-isopropylphosphino)ethane)PdCl2]
  参考文献：
  名称：

  Solution and Solid-State Structures of the Binuclear Zerovalent Palladium Complex [(dippe)Pd]₂(μ-dippe) (dippe = 1,2-Bis(diisopropylphosphino)ethane)

  摘要：

  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-31{H-1} NMR spectrum of 4; the solution structure and the solid-state structures are found to be very nearly identical.

  DOI：

  10.1021/om950825v

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
• 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.
• C–CN Bond Cleavage Using Palladium Supported by a Dippe Ligand
  作者：Lloyd Munjanja、Coralys Torres-López、William W. Brennessel、William D. Jones

  DOI：10.1021/acs.organomet.6b00304

  日期：2016.6.13

  The (dippe)palladium(0) fragment generated from [(dippe)Pd(mu-H)](2) (1) has been shown to form an intermediate eta(2)-nitrile complex with acetonitrile (dippe)Pd(eta(2)-C,N-CH3CN-BEt3) (2a) in the presence of BEt3 [(dippe = bis-diisopropylphosphino)ethane)]. On introducing a solution of 2a to 1 equiv of BPh3, rapid formation of (dippe)Pd(eta(2)-C,N-CH3CNBPh3) (2a') is observed. Heating 2a' at 100 degrees C in THF-d(8) results in the C-CN activation product 3a', (dippe)Pd(CH3)(CNBPh3). Reaction of 1 with benzonitrile in the presence of BEt3 gives the C-CN activation product (dippe)Pd(Ph)(CN-BEt3) (3b) exclusively. The complexes 2a, 2a', 3a', and 3b were characterized by H-1, P-31H-1}, and C-13H-1} NMR. spectroscopy, elemental analysis, IR spectroscopy, and X-ray diffraction.
• 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.
• Reactions of Electron-Rich Arylpalladium Complexes with Olefins. Origin of the Chelate Effect in Vinylation Catalysis
  作者：M. Portnoy、Y. Ben-David、I. Rousso、D. Milstein

  DOI：10.1021/om00021a021

  日期：1994.9

  Reaction of (dippp)Pd(Ph)Cl(1) with norbornene or styrene yields (dippp)PdCl2 (8) and (dippp)Pd(eta(2)-olefin). Kinetic follow-up reveals fast formation of (dippp)Pd(phenylnorbornyl)Cl (10), followed by its slow decomposition, with k(insertion) = 0.50 x 10(-3) L mol(-1) s(-1) and k(decomposition) = 0.90 X 10(-4) S-1. Phenylnorbornane and (with styrene) stilbenes are also formed. Faster reaction is observed with (dppp)Pd(Ph)Br (2) and faster still with (dippe)Pd(Cl (4) to yield, in the latter case, the stable (dippe)Pd(phenylnorbornyl)Cl (18). The rates of these reactions are strongly solvent dependent (DMF >> dioxane), are strongly retarded by added Cl-, and are unaffected by added phosphine, indicating that halide dissociation, followed by olefin coordination and rate-determining olefin insertion, are involved. In contrast, reaction of trans-(P(i)Pr(2)(n)Bu)(2)Pd(Ph)X (X = Cl, 5; X = Br, 6) with norbornene (or styrene) involves phosphine dissociation and leads to formation of (P(i)Pr(2)(n)Bu)(2)Pd(H)X. In the case of norbornene, beta-carbon elimination of the unobserved intermediate phenylnorbornyl complexes followed by beta-H elimination yields 1-methylene-2-phenylcyclohexenes. Complexes of the ligand dippb are unique in that both eta(1) and eta(2) coordination modes are easily accessible. While reaction products are similar to those obtained with dippp and dippe complexes, dependence of the reaction rate on reaction variables is intermediate between those observed for complexes of chelating and monodentate phosphines. The implications of these findings on catalysis are outlined.