[PdMe(NCMe)(1,2-bis(diphenylphosphino)ethane)](CF3SO3) | 139168-12-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [PdMe(NCMe)(1,2-bis(diphenylphosphino)ethane)](CF3SO3)
• 英文别名: [(dppe)PdMe(NCMe)](CF3SO3)
• CAS: 139168-12-0
• 化学式: CF₃O₃S*C₂₉H₃₀NP₂Pd
• 分子量: 710.002
• InChiKey: UKFDRTYJDXEAJA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [PdMe(NCMe)(1,2-bis(diphenylphosphino)ethane)](CF3SO3) 以 二氯甲烷 为溶剂， 生成 [Pd(COCH3)(bis(anisylimino)acenaphthene)(1,2-bis(diphenylphosphino)ethane)]CF3SO3
  参考文献：
  名称：

  合成，表征和离子钯的反应（II）含有以单齿配位方式的二齿氮配体复合物1 ，2

  摘要：

  新型离子络合物[Pd（Me）（p -An-BIAN）（LL）] SO 3 CF 3（LL= p -An-BIAN（bis（anisylimino）acenaphthene）（1a），phen（2a），dmphen（3a），dppe（4a），dppp（5a））是通过[Pd（Me）（NCMe）（p -An- BIAN ）] SO 3 CF 3与LL反应合成的。配合物1a的X射线晶体结构已确定并显示了扭曲的正方形平面几何形状，其中一个BIAN配体以双齿形式配位（PdN（1）= 2.037（4）Å;PdN（2）= 2.189（4）Å），并且有趣的是，另一个BIAN配体以不相同的方式出现（PdN（3）= 2.066（4）Å；PdN（4）= 2.714（6）Å）。混合的配体配合物[Pd（Me）（p -An-BIAN）（LL）] SO 3 CF 3（LL= phen（2a），dppe（

  DOI：

  10.1016/s0022-328x(98)00596-8
• 作为产物：
  描述：

  [1,1'-bis(diphenylphosphino)ethane(Pd(CH3)Cl)] 、 silver trifluoromethanesulfonate 在 乙腈 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 以82%的产率得到[PdMe(NCMe)(1,2-bis(diphenylphosphino)ethane)](CF3SO3)
  参考文献：
  名称：

  Influence of ligands and anions on the rate of carbon monoxide insertion into palladium-methyl bonds in the complexes (P-P)Pd(CH3)Cl and [(P-P)Pd(CH3)(L)]+SO3CF3- (P-P = dppe, dppp, dppb, dppf; L = CH3CN, PPh3)

  摘要：

  The preparation of the neutral complexes (P-P)Pd(CH3)Cl (P-P = 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), 1,1'-bis-(diphenylphosphino)ferrocene (dppf)) and the ionic complexes [(P-P)Pd(CH3)(CH3CN)]+SO3CF3-(P-P = dppe, dppp, dppb, dppf) is described. The ionic dppb complex was formed as a mixture of monomeric and oligomeric forms, which can be attributed to the length and the flexibility of the backbone of the ligand. The rate of CO insertion into the Pd-CH3 bond in these complexes has been studied. The rate was found to decrease in the order dppb almost-equal-to dppp > dppf for the neutral complexes with half-life times ranging from 18 to 36 min at 235 K and 25 bar of CO. The dppe complex reacted much slower with a half-life time of 170 min at 305 K. The rate of carbonylation of the Pd-CH3 bond in the cationic complexes was at least 10 times higher than those of the analogous neutral complexes, the order being dppb almost-equal-to dppp almost-equal-to dppf > dppe with half-life times < 1.5 min at 235 K, except for the dppe complex, for which a half-life time of 2.5 min was measured. Carbonylation of the ionic PPh3-coordinated complex [(dppp)Pd(CH3)(PPh3)]+-SO3CF3- was at least 2.5 times slower than that of the analogous CH3CN-coordinated cationic complex.

  DOI：

  10.1021/om00040a034

文献信息

• Pd-Catalyzed Copolymerization of Methyl Acrylate with Carbon Monoxide: Structures, Properties and Mechanistic Aspects toward Ligand Design
  作者：Akifumi Nakamura、Kagehiro Munakata、Shingo Ito、Takuya Kochi、Lung Wa Chung、Keiji Morokuma、Kyoko Nozaki

  DOI：10.1021/ja2003268

  日期：2011.5.4

  ethylene/CO copolymer. Both experimental and theoretical investigations were performed to clarify the superior nature of the palladium phosphine-sulfonate system compared to an unsuccessful conventional palladium diphosphine system: (i) The reversible insertion of CO was directly observed with the isolated alkylpalladium complexes, [o-((o-MeOC(6)H(4))(2)P)C(6)H(4)SO(3)}PdCH(CO(2)Me)CH(2)COMe], whereas

  提供了丙烯酸酯与一氧化碳 (CO) 交替共聚的全部细节，该共聚反应由带有膦磺酸盐双齿配体的钯物质催化。丙烯酸甲酯 (MA) 和 CO 的共聚物具有完全的区域规整性，其立体中心在甲醇存在下缓慢差向异构化。在乙烯的存在下，还制备了 MA/乙烯/CO 的三元共聚物。共聚物和三元共聚物的玻璃化转变温度高于乙烯/CO 共聚物的玻璃化转变温度。进行了实验和理论研究以阐明与不成功的常规二膦钯系统相比，钯膦-磺酸盐系统的优越性质：（i）用分离的烷基钯配合物直接观察到 CO 的可逆插入，[o-((o-MeOC(6)H(4))(2)P)C(6)H(4)SO(3)}PdCH(CO(2)Me)CH(2)COMe]，而在相应的带有 1,2-双（二苯基膦）乙烷 (DPPE) 的配合物上则没有观察到。(ii) 后续 MA 插入的过渡态，即催化循环的速率决定步骤，在膦-磺酸盐系统中的能量低于 DPPE 系统。这种稳定作
• Synthesis and reactions of heterodinuclear organopalladium–cobalt complexes acting as copolymerization catalyst for aziridine and carbon monoxide
  作者：Shin-ichi Tanaka、Hideko Hoh、Yoshifumi Akahane、Susumu Tsutsuminai、Nobuyuki Komine、Masafumi Hirano、Sanshiro Komiya

  DOI：10.1016/j.jorganchem.2006.04.044

  日期：2007.1

  A series of heterodinuclear acylpalladium-cobalt complexes having a bidentate nitrogen ligand, L-2(RCO)Pd-Co(CO)(4) (L-2 = bpy, R = Me (5), Ph (6); L-2 = tmeda, R = Me (7), Ph (8); L-2 = phen, R = Me (9), Ph (10)) are prepared by metathetical reactions of PdRIL2 with Na+[Co(CO)(4)](-) followed by treatment with CO. These complexes are characterized by NMR and IR spectroscopies and elemental analyses, and the molecular structures of 6, 8, and 9 are determined by X-ray structure analysis. Geometry at Pd is essentially square planar and the Cc atom is considered to have d(10) tetrahedral structure, where cobalt(-I) anion coordinates to palladium(II) cation. Heterodinuclear organopalladium-cobalt complexes are shown to catalyze copolymerization of aziridines and CO under mild conditions. Reaction of (dppe)MePd-Co(CO)(4) (1) with aziridine gives a cationic (aziridine)palladium(II) complex with [CO(CO)(4)](-) anion, [PdMe(aziridine)(dppe)](+)[CO(CO)(4)](-) (13). (c) 2006 Elsevier B.V. All rights reserved.