[{κ2-(P,O)-(2-anisyl)2PC6H4SO2O}Pd(Me)dmso] | 1107629-44-6

• 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-anisyl)2PC6H4SO2O}Pd(Me)dmso]
• 英文别名: [{κ₂-(P,O)-(2-anisyl)₂PC₆H₄SO₂O}Pd(Me)dmso]；[(κ2-P,O-2-(bis(2-methoxyphenyl)phosphino)benzenesulfonato)PdMe(dimethyl sulfoxide)]；[(κ2-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonato)PdMe(dimethylsulfoxide)]；[(κ2-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonato)PdMe(DMSO)]；[Pd(Me)(dmso)(κ2-(P,O)-2-(2-MeOC6H4)2PC6H4SO3)]2；[PdMe(κ2-P,O-2-(2-MeOC6H4)2PC6H4SO3)(dmso)]；(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)PdMe(dmso)
• CAS: 1107629-44-6
• 化学式: CH₃*C₂H₆OS*C₂₀H₁₈O₅PS*Pd
• 分子量: 600.99
• InChiKey: CUIMBAPAKPTVHS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  33.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  92.73
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  [{κ2-(P,O)-(2-anisyl)2PC6H4SO2O}Pd(Me)dmso] 在 C₃₂H₄₅⁽²⁾HO₅P₂PdS 作用下， 反应 1.5h， 生成 甲烷-d1
  参考文献：
  名称：

  中性膦硫磺酸钯聚合催化剂的活化和失活

  摘要：

  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

  DOI：

  10.1021/om300969d
• 作为产物：
  描述：

  [(κ2-P,O-2-[di(2-methoxyphenyl)phosphino]benzenesulfonato)PdMe](n) 、 二甲基亚砜 以 not given 为溶剂， 生成 [{κ2-(P,O)-(2-anisyl)2PC6H4SO2O}Pd(Me)dmso]
  参考文献：
  名称：

  Mechanistic Insights on Acrylate Insertion Polymerization

  摘要：

  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)Pd{kappa(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).

  DOI：

  10.1021/ja910760n

文献信息

• Insertion Homo‐ and Copolymerization of Diallyl Ether
  作者：Zhongbao Jian、Stefan Mecking

  DOI：10.1002/anie.201508930

  日期：2015.12.21

  by a palladium‐catalyzed insertion polymerization of diallyl ether as a monomer. An enhanced 2,1‐insertion of diallyl ether as compared to mono‐allyl ether retards the formation of an unreactive five‐membered cyclic O‐chelate (after 1,2‐insertion) that otherwise hinders further polymerization, and also enhances incorporation in ethylene polymers (20.4 mol %). Cyclic ether repeat units are formed selectively

  的聚合先前未解决的问题烯丙基单体CH 2 CHCH 2 X由二烯丙基醚作为单体的钯催化插入聚合克服。与单烯丙基醚相比，增强的二烯丙基醚的2,1插入可阻止未反应的五元环状O螯合物（1,2插入后）的形成，否则会阻碍进一步的聚合反应，并增强在乙烯中的掺入聚合物（20.4摩尔％）。环状醚重复单元是通过分子内单体的第二个烯丙基部分的插入而选择性地形成的（96％–99％）。这些特性甚至使均聚合以产生具有度DP的聚合的聚合物（聚二烯丙基醚）ñ ≈44。
• Direct and Tandem Routes for the Copolymerization of Ethylene with Polar Functionalized Internal Olefins
  作者：Min Chen、Changle Chen

  DOI：10.1002/anie.201913088

  日期：2020.1.13

  monomers and, recently, to 1,1-disubstituted ethylenes. Described in this contribution is a direct and tandem strategy to realize ethylene copolymerization with various 1,2-disubstituted ethylenes. The direct route is sensitive to sterics of both the comonomers and the catalyst. In the tandem route, ruthenium-catalyzed ethenolysis can convert 1,2-disubstituted ethylenes into terminal olefins, which

  过渡金属催化的乙烯与极性单体的共聚是一个极富挑战性的反应。经过数十年的研究，合适的共聚单体底物的范围已从特殊的极性单体扩展到基本的极性单体，最近又扩展到1,1-二取代的乙烯。在此贡献中描述了一种直接串联的策略，以实现与各种1,2-二取代的乙烯进行乙烯共聚。直接途径对共聚单体和催化剂的空间位敏感。在串联路线中，钌催化的乙烯分解可以将1,2-二取代的乙烯转化为末端烯烃，随后可以将其与乙烯共聚以提供极性官能化的聚烯烃。一锅，两步串联路线在处理具有挑战性的承印物时具有很高的通用性和效率。
• Palladium‐Catalyzed Insertion of Ethylene and 1,1‐Disubstituted Difunctional Olefins: An Experimental and Computational Study
  作者：Shahaji R. Gaikwad、Ketan Patel、Satej S. Deshmukh、Nilesh R. Mote、Rajkumar S. Birajdar、Satish P. Pandole、Jeetender Chugh、Samir H. Chikkali

  DOI：10.1002/cplu.202000309

  日期：2020.6

  Insertion or coordination copolymerization of ethylene with di‐substituted olefins is challenging and the choice of di‐substituted mono‐functional olefin versus di‐substituted di‐functional olefin (DDO) appears to be decisive. Here we show that DDO‐inserted species are amenable to ethylene insertion and polymerization. DDOs such as 2‐acetamidoacrylic acid (AAA), methyl 2‐acetamidoacrylate (MAAA), and

  乙烯与双取代烯烃的插入或配位共聚具有挑战性，选择双取代单官能烯烃与双取代双官能烯烃（DDO）似乎是决定性的。在这里，我们表明DDO插入的物种适合乙烯插入和聚合。DDOS如2- acetamidoacrylic酸（AAA），甲基2-乙酰氨基（MAAA），和2-氰基丙烯酸酯（ECA）用钯复合物处理[P∧O} PDME（L）]（P∧O=κ 2 -P，O-Ar 2 PC 6 H 4 SO 2 O，Ar = 2-MeOC 6 H 4 ; L = C 2 H 6OS）和中等插入率（高达37％）的各个插入中间体的存在。这些中间体暴露于乙烯，并分离和表征了相应的乙烯插入产物。与三种模型化合物的仔细比较证实了乙烯的插入和聚合。因此，结合实验和计算研究表明，DDO插入的物质可能会发生乙烯插入和聚合反应。
• 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)