[κ²-(anisyl)₂P,O]Pd(CH₃)(pyridine) | 925941-63-5

• 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: [κ²-(anisyl)₂P,O]Pd(CH₃)(pyridine)
• 英文别名: [Pd(pyridine)Me(2-(bis(2-methoxyphenyl)phosphonium)benzenesulfonate)]；[(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)PdMe(pyridine)]；2-bis(2-methoxyphenyl)phosphanylbenzenesulfonate;carbanide;palladium(2+);pyridine
• CAS: 925941-63-5
• 化学式: C₂₆H₂₆NO₅PPdS
• 分子量: 601.956
• InChiKey: CDHFKMVWGBIIMM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  35
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  96.9
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [κ²-(anisyl)₂P,O]Pd(CH₃)(pyridine) 在 B(C₆F₅)3 作用下， 以 not given 为溶剂， 生成 [(κ2-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonato)PdMe](n)
  参考文献：
  名称：

  甲基丙烯酸酯在插入聚合中的反应性

  摘要：

  乙烯通过配合物聚合 [{(P^O)PdMe(L)}] (P^O = κ(2)-(P,O)-2-(2-MeOC(6)H(4))(2 )PC(6)H(4)SO(3))) 提供不含任何甲基丙烯酸甲酯 (MMA) 衍生单元的均聚聚乙烯，即使存在大量 MMA 也是如此。在化学计量研究中，通过从 [({(P^O)Pd(Me)Cl}μ-Na)(2)] 中提取卤化物产生的反应性 {(P^O)Pd(Me)L} 片段将 MMA 插入 1 ,2- 以及 2,1-模式。1,2-插入产物通过羰基的配位形成稳定的五元螯合物。MMA 插入的热力学参数为 ΔH(++) = 69.0(3.1) kJ mol(-1) 和 ΔS(++) = -103(10) J mol(-1) K(-1)（1 ,2- 和 2,1-插入），与 ΔH(++) = 48.5(3.0) kJ mol(-1) 和 ΔS(++) = -138(7) J mol(-1)

  DOI：

  10.1021/ja107538r
• 作为产物：
  描述：

  triethylammonium chloro(2-(bis(2-methoxyphenyl)phosphonium)benzenesulfonate)methylpalladium(II) 在 Ag p-toluenesulfonate 作用下， 以 二氯甲烷 为溶剂， 生成 [κ²-(anisyl)₂P,O]Pd(CH₃)(pyridine)
  参考文献：
  名称：

  Ligand effects in the non-alternating CO–ethylene copolymerization by palladium(ii) catalysis

  摘要：

  在本文中，我们报道了中性 PdII 配合物与膦磺酸配体双（邻甲氧基苯基）膦基亚苯基磺酸酯和双（邻甲氧基苯基）膦基乙烯磺酸酯催化非交替 CO-C2H4 共聚的比较研究。前一种配体具有较低的骨架柔韧性，已被发现可以形成更具活性的催化剂，并产生具有更高分子量和更高乙烯外掺入量的聚酮。原位高压核磁共振研究使我们能够首次在非交替共聚循环中截获 PdII（膦磺酸盐）β-螯合物，而模型有机金属反应有助于证明 PdII（膦磺酸盐） ) 片段不会形成稳定的羰基复合物。已发现β-螯合物的打开是任一共聚单体的可行过程，这与完美交替共聚的PdII（螯合二膦）催化剂的行为形成对比。

  DOI：

  10.1039/b711280g

文献信息

• Activation and Deactivation of Neutral Palladium(II) Phosphinesulfonato Polymerization Catalysts
  作者：Thomas Rünzi、Ulrich Tritschler、Philipp Roesle、Inigo Göttker-Schnetmann、Heiko M. Möller、Lucia Caporaso、Albert Poater、Luigi Cavallo、Stefan Mecking

  DOI：10.1021/om300969d

  日期：2012.12.10

  3CH3)P,O] (13) isolated from pressure reactor polymerization experiments. In addition, ESI-MS analyses of reactor polymerization filtrates indicate the presence of (odd- and even-numbered alkyl)(anisyl)phosphine sulfonates (14) and their respective phosphine oxides (15). Furthermore, 2-(vinyl)anisole was detected in NMR tube and reactor polymerizations, which results from ethylene insertion into a

  13 C标记的乙烯聚合（预）催化剂[κ 2 - （茴香基）2 P，O ]将Pd（13 CH 3）（L）（1- 13 CH 3 -L）（L =吡啶，DMSO）基于二（2-茴香基）膦苯磺酸盐用于评估13个CH 3基团向形成的聚乙烯中的结合程度。可变反应时间的聚合显示出约。在已经经过1分钟的聚合时间后，在聚合物中发现了60–85％的13 C-标记，这提供了证据表明催化剂前体1- 13 CH 3 -L之间存在预平衡活性物种1- 13 CH 3-（乙烯）链增长快。引发链增长的1- 13 CH 3 -L分数可能高于13 C-标记的聚合物链端确定的60-85％，因为（a）链行走导致13 C-链内掺入。标记，（b）通过形成饱和（和部分挥发性）烷烃而导致不可逆的催化剂失活减少了掺入聚合物中的13 CH 3基团的量，以及（c）钯键结合的13 CH 3基团，以及更一般的钯键结合的烷基（聚合物基）链，通过还原消除
• Inhibitory Role of Carbon Monoxide in Palladium(II)-Catalyzed Nonalternating Ethene/Carbon Monoxide Copolymerizations and the Synthesis of Polyethene-<i>block</i>-poly(ethene-<i>alt</i>-carbon monoxide)
  作者：David K. Newsham、Sachin Borkar、Ayusman Sen、David M. Conner、Brian L. Goodall

  DOI：10.1021/om700523m

  日期：2007.7.1

  palladium-based system for the living homopolymerization of ethene, as well as the living copolymerization of ethene with carbon monoxide. We demonstrate this by the synthesis of polyethene-block-poly(ethene-alt-carbon monoxide). In addition, it has been possible to monitor chain growth by sequential insertions of carbon monoxide and ethene into palladium−carbon bonds. The mechanistic studies have also

  我们报告了第一个明确定义的钯基体系，用于乙烯的活性均聚以及乙烯与一氧化碳的活性共聚。我们通过polyethene-的合成表明此块-聚（ethene- ALT碳上一氧化碳）。此外，通过将一氧化碳和乙烯顺序插入钯碳键中，可以监测链增长。机理研究还使我们能够找到迄今尚未得到充分理解的普遍无法获得低一氧化碳含量的烯烃/一氧化碳共聚物的原因。
• Palladium-Catalyzed Nonalternating Copolymerization of Ethene and Carbon Monoxide: Scope and Mechanism
  作者：Rong Luo、David K. Newsham、Ayusman Sen

  DOI：10.1021/om9008235

  日期：2009.12.28

  nonalternating ethene/carbon monoxide copolymers with very low carbon monoxide content were synthesized using a neutral palladium catalyst bearing a phosphine-sulfonate ligand. The ratio of the binding affinities of carbon monoxide and ethene to the palladium chelate complex (P∩SO3)PdCH2CH2C(O)CH3 has been determined by NMR spectroscopy to be ∼50:1 at 25 °C. The migratory insertions of ethene and carbon monoxide

  使用带有膦磺酸盐配体的中性钯催化剂合成了一系列一氧化碳含量非常低的非交替乙烯/一氧化碳共聚物。一氧化碳和乙烯的所述钯螯合物的结合亲和力的比值（P ∩ SO 3）PDCH 2 CH 2 Ç （O）CH 3已经通过NMR光谱测定为〜50：1，在25℃。乙烯和一氧化碳的迁移插入到钯甲基络合物（P ∩ SO 3）PDCH 3（PY）也已经通过NMR光谱法检测，给予以下激活参数：Δ ģ⧧（25°C）= 21.7 kcal mol -1（ΔH⧧ = 17.7（1）大卡摩尔-1和ΔSinsertion = -13.6（4）eu）用于乙烯插入; △ G⧧（25°C）= 13.0 kcal mol -1（ΔH⧧ = 16.6（8）大卡摩尔-1和ΔSinsertion = 20（434）eu），用于插入一氧化碳。我们的研究表明，乙烯和一氧化碳的结合亲和力异常小，在决定共聚物组成方面起着重要作用。
• Mechanistic Insights on Acrylate Insertion Polymerization
  作者：Damien Guironnet、Lucia Caporaso、Boris Neuwald、Inigo Göttker-Schnetmann、Luigi Cavallo、Stefan Mecking

  DOI：10.1021/ja910760n

  日期：2010.3.31

  Complexes [(P boolean AND O)PdMe}(n)] (1(n); P boolean AND O = kappa(2)-P,O-Ar2PC6H4SO2O with Ar = 2-MeOC6H4) are a single-component precursor of the (P boolean AND O)PdMe fragment devoid of additional coordinating ligands, which also promotes the catalytic oligomerization of acrylates. Exposure of 1(n) to methyl acrylate afforded the two diastereomeric chelate complexes [(P boolean AND O)Pdkappa(2)-C,O-CH(C(O)OMe)CH2CH(C(O)OMe)CH2CH3}] (3-meso and 3-rac) resulting from two consecutive 2,1-insertions of methyl acrylate into the Pd-Me bond with the same or opposite stereochemistry, respectively, in a 3:2 ratio as demonstrated by comprehensive NMR spectroscopic studies and single crystal X-ray diffraction. These six-membered chelate complexes are direct key models for intermediates of acrylate insertion polymerization, and also ethylene-acrylate copolymerization to high acrylate content copolymers. Studies of the binding of various substrates (pyridine, dmso, ethylene and methyl acrylate) to 3-meso and 3-rac show that hindered displacement of the chelating carbonyl moiety by pi-coordination of incoming monomer significantly retards, but does not prohibit, polymerization. For 3-meso,3-rac + C2H4 reversible arrow 3-meso-C2H4, 3-rac-C2H4 an equilibrium constant K(353 K) approximate to 2 x 10(-3) L mol(-1) was estimated. Reaction of 3-meso, 3-rac with methyl acrylate afforded higher insertion products [(P boolean AND O)Pd(C4H6O2)(n)Me] (n = 3, 4) as observed by electrospray ionization mass spectrometry (ESI-MS). Theoretical studies by DFT methods of consecutive acrylate insertion provide relative energies of intermediates and transition states, which are consistent with the aforementioned experimental observations, and give detailed insights to the pathways of multiple consecutive acrylate insertions. Acrylate insertion into 3-meso,3-rac is associated with an overall energy barrier of ca. 100 kJ mol(-1).
• Insertion Polymerization of Acrylate
  作者：Damien Guironnet、Philipp Roesle、Thomas Rünzi、Inigo Göttker-Schnetmann、Stefan Mecking

  DOI：10.1021/ja808017n

  日期：2009.1.21

  Multiple insertions of acrylate in copolymerization with ethylene, and an insertion homooligomerization of methyl acrylate were observed for the first time. Key to these findings, and to mechanistic insights reported, are labile-substituted complexes as catalyst precursors.