[(κ2-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonato)PdMe](n) | 1233194-46-1

• 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-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonato)PdMe](n)
• CAS: 1233194-46-1
• 化学式: C₂₁H₂₁O₅PPdS
• 分子量: 522.855
• InChiKey: QUNJVAUNKQFDMR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  29.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  75.66
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  [(κ2-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonato)PdMe(DMF)] 以 二氯甲烷 为溶剂， 生成 [(κ2-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonato)PdMe](n)
  参考文献：
  名称：

  丙烯酰胺极性单体插入聚合的机理研究

  摘要：

  N-异丙基丙烯酰胺 (NIPAM)、N,N-二甲基丙烯酰胺 (DMAA) 和 2-乙酰氨基乙基丙烯酸酯 (AcAMEA) 使用 [(P^O)PdMe(DMSO)] (1-DMSO; P^O) 与乙烯共聚= κ(2)-P,O-Ar(2)PC(6)H(4)SO(2)O，Ar = 2-MeOC(6)H(4)) 作为催化剂前体。使用不可聚合的极性添加剂进行的抑制研究表明，游离酰胺的可逆 κ-O 配位显着延缓了聚合反应。聚合的延迟增加的顺序是乙酸乙酯≪甲乙砜<乙腈

  DOI：

  10.1021/ja207110u

文献信息

• Limits of Activity: Weakly Coordinating Ligands in Arylphosphinesulfonato Palladium(II) Polymerization Catalysts
  作者：Boris Neuwald、Franz Ölscher、Inigo Göttker-Schnetmann、Stefan Mecking

  DOI：10.1021/om3000339

  日期：2012.4.23

  analyses. Complexes derived from weakly coordinating phosphine oxides have eluded isolation due to loss of phosphine oxide and formation of barely soluble multinuclear palladium complexes 1n by bridging coordination of the sulfonate group to various Pd centers. Hence, the (P∧O)PdMe fragment 1 exhibits an intrinsic limitation with respect to coordination of weak donors. Species 1 generated in situ in the

  各种膦氧化物的协调强度OPR 3朝向的烯烃聚合催化剂（P ∧ O）PDME（P ∧ O =κ 2 - P，O -Ar 2 P c ^ 6 ħ 4 SO 2 ö用Ar = 2- MeOC 6 ħ 4）与DMso相比已经确定。反应1-DMso + L⇆1 -L + DMso的平衡常数K L范围从3.5（对于富电子的OPBu 3）到10 –3（对于电子贫乏的OP（p -CF 3）C 6 H 4）3。络合物从更强配位的膦氧化物衍生的，即，[（P ∧ O）PDME（L）]（1-L为：L = OPBu 3，OPOct 3，OPPh 3）已被分离和完全表征。另外，通过X射线衍射分析来分析1-OPBu 3和1-OPPh 3。由于膦氧化物的损失以及通过将磺酸盐基团的配位桥接到各个Pd中心上而形成的几乎不溶的多核钯配合物1 n，衍生自弱配位的氧化膦的配合物无法进行分离。因此，（P∧ O）PDME片段1所表现出
• Reactivity of Methacrylates in Insertion Polymerization
  作者：Thomas Rünzi、Damien Guironnet、Inigo Göttker-Schnetmann、Stefan Mecking

  DOI：10.1021/ja107538r

  日期：2010.11.24

  Polymerization of ethylene by complexes [(P^O)PdMe(L)}] (P^O = κ(2)-(P,O)-2-(2-MeOC(6)H(4))(2)PC(6)H(4)SO(3))) affords homopolyethylene free of any methyl methacrylate (MMA)-derived units, even in the presence of substantial concentrations of MMA. In stoichiometric studies, reactive (P^O)Pd(Me)L} fragments generated by halide abstraction from [((P^O)Pd(Me)Cl}μ-Na)(2)] insert MMA in a 1,2- as well

  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)
• 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).