[(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)Pd(κ2-C,O-CH(COOMe)CH2CH(COOMe)CH2CH3)] | 1233194-69-8

• 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)Pd(κ2-C,O-CH(COOMe)CH2CH(COOMe)CH2CH3)]
• CAS: 1233194-69-8
• 化学式: C₂₉H₃₃O₉PPdS
• 分子量: 695.035
• InChiKey: INGZGRDGQKJTKC-IXSARBFQSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)Pd(κ2-C,O-CH(COOMe)CH2CH(COOMe)CH2CH3)] 、 二甲基亚砜 以 not given 为溶剂， 生成
  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
• 作为产物：
  描述：

  [(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)PdMeCl(μ-Na))2] 、 丙烯酸甲酯（MA） 在 AgBF₄ 作用下， 以 CH₂Cl₂ 为溶剂， 生成 [(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)Pd(κ2-C,O-CH(COOMe)CH2CH(COOMe)CH2CH3)] 、 [(κ2-P,O-(2-MeOC6H4)2PC6H4SO2O)Pd(κ2-C,O-CH(COOMe)CH2CH(COOMe)CH2CH3)]
  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