[(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)PdMe(2,6-lutidine)] | 925941-62-4

• 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-MeOC6H4)2PC6H4SO2O)PdMe(2,6-lutidine)]
• 英文别名: 2-bis(2-methoxyphenyl)phosphanylbenzenesulfonate;carbanide;2,6-dimethylpyridine;palladium(2+)
• CAS: 925941-62-4
• 化学式: C₂₈H₃₀NO₅PPdS
• 分子量: 630.01
• InChiKey: XHHRREFWTBBYKE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.51
• 重原子数：
  37
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 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-P,O-(2-MeOC6H4)2PC6H4SO2O)PdMe(2,6-lutidine)] 以 甲苯 为溶剂， 生成 Pd(n-Pr)(2,6-lutidine)(2-(bis(2-methoxyphenyl)phosphino)benzenesulfonato)
  参考文献：
  名称：

  膦-磺酸钯配合物催化形成线性聚乙烯链的机理研究：实验与理论研究

  摘要：

  从 Pd 膦-磺酸盐复合物开始的线性聚乙烯传播，Pd(CH(3))(L)(Ar(2)PC(6)H(4)SO(3)) (L = 2,6-二甲基吡啶，Ar = o-MeOC(6)H(4) (2a) 和 L = 吡啶，Ar = Ph (2b))，通过实验和理论进行了研究。实验上，高度线性聚乙烯是用 Pd(CH(3))(L)(Ar(2)PC(6)H(4)SO(3)) 配合物 2a 和 2b 获得的。作为在以甲基钯配合物为原料的钯中心上的乙烯低聚反应的结果，检测到长链烷基取代的钯配合物 (3) 的形成。此外，明确定义的乙基和丙基配合物（6（Et）和 6（Pr））被合成为稳定的正烷基钯配合物。尽管存在β-氢，但在所有情况下产生1-烯烃的β-氢化物消除非常缓慢或可忽略不计。另一方面，在甲基钯/膦-磺酸盐络合物2a存在下1-己烯的异构化表明该催化剂体系实际上经历了β-氢化物消除和重新插入以释放内部烯烃。在理论方面，基于起始模型复合物

  DOI：

  10.1021/ja9047398
• 作为产物：
  描述：

  2,6-二甲基吡啶 、 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 以68%的产率得到[(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)PdMe(2,6-lutidine)]
  参考文献：
  名称：

  膦磺酸钯配合物催化乙烯丙烯腈线性共聚物的形成

  摘要：

  乙烯和丙烯腈的线性共聚物使用带有膦-磺酸盐双齿配体的钯配合物制备。13C NMR 光谱首次检测到位于线性聚乙烯主链中的丙烯腈单元。使用分离的钯配合物（例如 3）的催化剂体系表现出比原位生成程序高得多的共聚活性，并且共聚物的分子量和丙烯腈的掺入取决于钯配合物。获得的乙烯和丙烯腈的线性共聚物在比支化共聚物更高的温度下熔化。

  DOI：

  10.1021/ja0725504

文献信息

• Synthesis of Polyethylene with In‐Chain α,β‐Unsaturated Ketone and Isolated Ketone Units: Pd‐Catalyzed Ring‐Opening Copolymerization of Cyclopropenone with Ethylene
  作者：Xiaoming Wang、Falk William Seidel、Kyoko Nozaki

  DOI：10.1002/anie.201906990

  日期：2019.9.9

  copolymerization of ethylene with cyclopropenone, leading to incorporation of C3 units with functional groups, α,β-unsaturated ketones, in the chain. Coordination-insertion of the carbonyl group and ring opening of the strained three-membered ring are proposed as the key steps in the mechanism. Under different reaction conditions an isolated ketone structure was afforded as the major carbonyl unit, and could

  尽管可以通过非官能化烯烃与极性官能单体的过渡金属催化配位共聚合将各种官能化单元掺入聚烯烃中，但是掺入的官能团在很大程度上限于来自CO的C1单元或来自乙烯基单体的C2单元。此处报道的是Pd催化的乙烯与环丙烯酮的共聚反应，导致链中带有官能团α，β-不饱和酮的C3单元的结合。羰基的配位插入和应变三元环的开环被认为是该机理的关键步骤。在不同的反应条件下，提供了分离的酮结构作为主要的羰基单元，并且可以通过乙烯与由环丙烯酮原位形成的CO的共聚反应生成。
• 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
• High Density Polyethylenes Bearing Isolated In‐Chain Carbonyls**
  作者：Shan Tang、Falk William Seidel、Kyoko Nozaki

  DOI：10.1002/anie.202110957

  日期：2021.12.13

  Incorporation of a low CO content in the main-chain of polyethylene along with remarkable isolated carbonyl selectivity was achieved via palladium catalyzed copolymerization of ethylene with metal carbonyls. This polyethylene copolymer retained the main physical properties of high-density polyethylene (HDPE), while treating the obtained copolymer with UV light resulted in partial degradation. Therefore

  通过钯催化乙烯与金属羰基化合物的共聚，在聚乙烯主链中掺入低 CO 含量以及显着的分离羰基选择性。这种聚乙烯共聚物保留了高密度聚乙烯 (HDPE) 的主要物理特性，同时用紫外线处理所得共聚物会导致部分降解。因此，合成材料可作为比传统聚乙烯材料更环保的替代塑料。
• 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).