[Pd(1,3-bis(diphenylphosphino)propane)(OAc)2] | 149796-59-8

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Pd(1,3-bis(diphenylphosphino)propane)(OAc)2]
• 英文别名: Pd(1,3-bis(diphenylphosphanyl)propane)(OAc)2；bis(acetato)(1,3-bis(diphenylphosphine)propane)palladium(II)；[(1,3-bis(diphenylphosphino)propane)Pd(acetate)2]；[Pd(1,2-bis(diphenylphosphino)propane)(O2CCH3)2]；[Pd(OAc)2(1,2-bis(diphenylphosphino)propane)]；[Pd(OAc)2(dppp)]；3-diphenylphosphanylpropyl(diphenyl)phosphane;palladium(2+);diacetate
• CAS: 149796-59-8
• 化学式: C₃₁H₃₂O₄P₂Pd
• 分子量: 636.96
• InChiKey: KCQJJIGUZDDNID-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  38
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险性防范说明：
  P261,P280,P301+P312,P302+P352,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

反应信息

• 作为反应物：
  描述：

  [Pd(1,3-bis(diphenylphosphino)propane)(OAc)2] 以 N,N-二甲基甲酰胺 为溶剂， 生成 钯
  参考文献：
  名称：

  由Pd（OAc）2和二齿膦配体（dppp）形成的钯（0）配合物及其氧化加成反应性

  摘要：

  由Pd（OAc）2和二齿膦如dppp（1,3-双（二苯基膦基）丙烷）自发生成Pd 0络合物。dppp是还原剂，被氧化成半氧化物dppp（O）。分子内还原步骤是可逆的。在2当量的dppp，水和碱（NEt 3）存在下，定量形成了稳定的Pd 0络合物。PhI的氧化加成得到阳离子络合物PhPd（dppp）（dppp（O））+，其中dppp（O）表现为单齿配体。PhPd（OAC）（DPPP）形成在加入ACO的存在- 。PhI的氧化加成反应是一个复杂的反应，只有在添加AcO-的情况下，才对其动力学进行了研究。。它涉及由AcO连接的反应性二聚或/和单体Pd 0络合物-其相对反应性是PhI浓度的函数。

  DOI：

  10.1021/om0101137
• 作为产物：
  描述：

  1,3-双(二苯基膦)丙烷 、 palladium diacetate 以 甲苯 为溶剂， 以77%的产率得到[Pd(1,3-bis(diphenylphosphino)propane)(OAc)2]
  参考文献：
  名称：

  2-吡啶-2-基取代的1,3-双（二苯基膦基）丙烷的钯配合物：一氧化碳与乙烯进行室温共聚合的高活性催化剂

  摘要：

  2,2'-二取代的1,3-双（二苯基膦基）丙烷衍生物[XC（Me）（CH 2 PPh 2）2 ]（X = 2-py，1a ; X = CH 2 OMe，1b ; X = Ph ，1c）及其相应的钯配合物[（P-P）PdCl 2 ]（2a - c），[（P-P）Pd（OAc）2 ]（3a - c），[{2-甲基-2-吡啶-2-基-1,3-双（二苯基膦基）丙烷} PdClMe]（4a）和[{（S）-（+）- N，N-二甲基-α-甲基苄胺-C，N} Pd {2- MeOCH 2 CMe（CH 2已经制备并表征了PPh 2）2 }] [ClO 4 ]（5b）。2-甲基-2-吡啶-2-基-1,3-双（二苯基膦基）丙烷（1a）的钯（II）络合物对乙烯和一氧化碳的室温共聚反应具有很高的活性，在我们的条件下，明显比基于1,3-双（二苯基膦基）丙烷（dppp），1b和1c的系统更具活性。由dppp，1b和1

  DOI：

  10.1021/om020301c
• 作为试剂：
  描述：

  N-Boc-2-碘苯胺 在 盐酸 、 六甲基磷酰三胺 、 copper(l) iodide 、 四(三苯基膦)钯 、 [Pd(1,3-bis(diphenylphosphino)propane)(OAc)2] 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二甲基亚砜 为溶剂， 70.0 ℃ 、101.33 kPa 条件下， 生成 Methyl [1,4]benzodioxino[3,2-c]quinoline-6-carboxylate
  参考文献：
  名称：

  Convenient syntheses of substituted 7,12-dioxa-benzo[a]anthracenes and 7,12-dioxa-5-aza-benzo[a]anthracenes

  摘要：

  The syntheses of 7,12-Dioxa-benzo[a]anthracenes bearing in C-6 a carboxymethyl group and 5-aza analogues are described. The key steps are intramolecular cyclisations of 3-arylbenzo[1,4]dioxin-2-diethylcarboxamides and palladium catalysed methoxycarbonylation of aryl triflates. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(97)10756-0

文献信息

• Self-Assembly and Anion Encapsulation Properties of Cavitand-Based Coordination Cages
  作者：Federica Fochi、Paola Jacopozzi、Elina Wegelius、Kari Rissanen、Pietro Cozzini、Elena Marastoni、Emilia Fisicaro、Paola Manini、Roel Fokkens、Enrico Dalcanale

  DOI：10.1021/ja0103492

  日期：2001.8.1

  cavitand component. The crystal structure of cage 7d revealed the presence of a single triflate anion encapsulated. Guest competition experiments revealed that the encapsulation preference of cages 7b,d follows the order BF(4)(-) > CF(3)SO(3)(-) >> PF(6)(-) at 300 K. ES-MS experiments coupled to molecular modeling provided a rationale for the observed encapsulation selectivities. The basic selectivity pattern

  已经通过自组装程序合成了两种新型的基于腔体的协调笼 7a--j 和 8a--d。控制笼自组装 (CSA) 的主要因素已确定为 (i) 螯合配体和金属前体之间的 P--M--P 角接近 90 度，(ii) Pd 和 Pt 作为金属中心， (iii) 弱配位的反离子，和 (iv) 四齿空腔配体的预组织。量热测量和动态 (1) H 和 (19) F 核磁共振实验表明 CSA 是熵驱动的。平衡笼低聚物的温度范围由空腔组分的预组织水平决定。笼子 7d 的晶体结构显示存在单个被封装的三氟甲磺酸盐阴离子。来宾竞争实验表明，笼子 7b 的封装偏好，d 遵循 BF(4)(-) > CF(3)SO(3)(-) >> PF(6)(-) 在 300 K 的顺序。 ES-MS 实验与分子建模相结合为观察到的提供了基本原理封装选择性。遵循客体溶剂化焓的基本选择性模式会因腔的大小和形状而改变，仅在 BF(4)(-) 的情况下才允许辅助溶剂分子进入。
• Alumoxanes as Cocatalysts in the Palladium-Catalyzed Copolymerization of Carbon Monoxide and Ethylene:  Genesis of a Structure−Activity Relationship
  作者：Yoshihiro Koide、Simon G. Bott、Andrew R. Barron

  DOI：10.1021/om9508492

  日期：1996.4.30

  cocatalytic activity to be [(tBu)Al(μ3-O)]7 > [(tBu)Al(μ3-O)]6 > [(tBu)Al(μ3-O)]9 ≫ [(tBu)7Al5(μ3-O)3(μ-OH)2]. This observed cocatalytic activity correlates with the predicted latent Lewis acidity of the alumoxanes. A discussion of the palladium−alumoxane complex is presented with respect to the model compound [(tBu)6Al6(μ3-O)4(μ-OH)2(μ-O2CCCl3)2], prepared by the reaction of [(tBu)Al(μ3-O)]6 with HO2CCCl3.

  一氧化碳和乙烯的钯-催化的共聚得到的聚酮聚合物，[CH 2 CH 2 C（O）] Ñ，已经通过使用任一（DPPP）的加入Pd（OAc）来实现2或（DPPP）的Pd [C （O）吨卜]在氯的存在下，叔丁基铝氧烷，[（吨丁基）铝（μ 3 -O）] ñ（ñ = 6，7,9）或[（吨丁基）7的Al 5（ μ 3 -O）3（μ-OH）2]助催化剂。确定了对铝氧烷和钯浓度的催化活性，铝氧烷结构以及膦配体的身份的影响。显示铝氧烷的功能取决于钯催化剂前体的选择。铝氧烷与（DPPP）Pd [C（O）t Bu] Cl一起提取氯化物，直接制得具有催化活性的阳离子钯络合物。相反，铝氧烷最初将（DPPP）Pd（OAc）2中的钯烷基化，随后提取出剩余的乙酸根阴离子，得到活性的阳离子钯络合物。催化活性高度依赖于铝氧烷的结构。的比较研究表明助催化活性是[（吨丁基）铝（μ 3 -O）]7 > [（吨丁基）铝（μ 3 -O）]
• Metal Trimethylsilylthiolates for the Synthesis of Trinuclear MnPd₂ Complexes
  作者：Kyle N. W. Rozic、Mahmood Azizpoor Fard、Bahareh Khalili Najafabadi、John F. Corrigan

  DOI：10.1002/zaac.201700179

  日期：2017.8.16

  The manganese(II)-palladium(II)-sulfide complex [MnCl2(μ3-S)2Pd2(dppp)2] (2) was prepared from the reaction of [PdCl2(dppp)] with [Li(N,N'-tmeda)]2[Mn(SSiMe3)4] (2) in a 2:1 ratio under mild conditions. The new trimethylsilylthiolate complex [Pd(dppp)(SSiMe3)2] (3) was synthesized from the reaction of [Pd(dppp)(OAc)2] with two equivalents of Li[SSiMe3]; this was then used in a reaction with [Mn(CH3CN)2(OTf)2]

  锰(II)-钯(II)-硫化物复合物[MnCl2(μ3-S)2Pd2(dppp)2] (2) 由[PdCl2(dppp)]与[Li(N,N'- tmeda)]2[Mn(SSiMe3)4] (2) 在温和条件下以 2:1 的比例混合。新的三甲基甲硅烷基硫醇盐络合物 [Pd(dppp)(SSiMe3)2] (3) 是由 [Pd(dppp)(OAc)2] 与两当量的 Li[SSiMe3] 反应合成的；然后将其用于与 [Mn(CH3CN)2(OTf)2] 的反应以形成锰 (II)-钯 (II)-硫化物簇 [Mn(OTf)(thf)2(μ3-S)2Pd2( dppp)2]OTf (4)。
• Studies on palladium-bisphosphine catalyzed alternating copolymerization of CO and ethylene
  作者：He-Kuan Luo、Yuan Kou、Xi-Wen Wang、Da-Gang Li

  DOI：10.1016/s1381-1169(99)00258-7

  日期：2000.2

  Palladium(II)-bisphosphine catalyzed copolymerization of CO and ethylene was studied in detail. The results showed that DPPPr/Pd(II) mole ratio, CF3COOH/Pd(II) mole ratio and solvent greatly influence the catalytic activity. Solvent effects were studied and in detail through end group analysis. With high pressure in situ H-1-NMR technique, the signals of coordinated ethylene at 4.4 ppm and methylene linked with Pd(II) (Pd-CH2-) at 0.6 ppm were observed. With high-pressure in situ IR technique three palladium carbonyl absorptions were observed generated at 1638 cm(-1), 1616 cm(-1) and 1970 cm(-1), which may be assigned to three intermediates (3) (5) (6). With the above results, the copolymerization mechanisms were discussed. High-pressure in situ P-31-NMR experimental result showed that only mono-chelate ring complex(1) was produced when DPPPr/Pd(II) = 1; only bis-chelate ring complex (2) was produced when DPPPr/Pd(II) = 2; equimolar complex (1) and (2) were produced when DPPPr/Pd(II)=1.5. Extended X-ray absorption fine structure (EXAFS) was used to calculate the coordination number (CN) and shell radius (R, in Angstrom) of complexes (DPPPr)Pd(OCOCF3)(2) (a), (DPPBu)Pd(OCOCF3)(2) (b), (DPPEt)Pd(OCOCF3)(2) (c), (DPPPr)(2)Pd(OCOCF3)(2) (e), and two catalyst solutions or methanol freshly taken before and in the middle of copolymerization (named S1 and S2, respectively). The Pd-P bond length of complexes (a) (b) (c) are 2.25(3) Angstrom, 2.33(3) Angstrom, and 2.38(2) Angstrom, respectively, Pd-O bond length of complexes (a) (b) (c) are 2.07(3) Angstrom, 2.06(2) Angstrom and 2.05(3) Angstrom, respectively. In the order of complexes (a) (b) (c), the catalytic activity increases with Pd-P bond decreasing and Pd-O bond increasing, which may show that the chelate ring is more stable, the anions can go away more easily, and the corresponding catalyst is more efficient. The coordination number of two catalyst solutions S1 and S2 are increased by 1.9 and 0.9 compared with solid complex (a), which may show that 18-electron and five-coordinated pyramidal intermediates were produced and existed in the system besides 16-electron and four-coordinated square planar intermediates. (C) 2000 Elsevier Science B.V. All rights reserved.
• Mechanistic Studies of Alkene/CO Polymerization with Palladium Complexes Promoted by B(C₆F₅)₃
  作者：Graham K. Barlow、Jane D. Boyle、Neil A. Cooley、Talit Ghaffar、Duncan F. Wass

  DOI：10.1021/om990911l

  日期：2000.4.1

  The reaction of Pd(dppp)(OAc)(2) [dppp = 1,3-bis(diphenylphosphino)propane] with B(C6F5)(3) in situ gives an efficient catalyst for alkene/CO polymerization in aprotic media. The borane is consumed during the polymerization, and its fluoroaryl groups are incorporated into the polymer chain ends. In the absence of the monomers the catalyst components react to give palladium(II)-pentafluoroaryl complexes formulated as Pd(dppp)(C6F5)[B(C6F5)(3)](y)OH} (y = 1, 3a; y = 2, 3b). Complex 3a can be isolated, albeit as an impure solid, and is itself a catalyst for the reaction. In light of these results a novel chain initiation process for the polymerization is proposed, involving insertion of monomers into a fluoroarylpalladium complex formed by aryl transfer from the borane to a palladium(II) complex. This facile initiation step, combined with the catalyst stability engendered by the presence of strong Bronsted acids, explains the effectiveness of this catalyst system in aprotic media.