Pd(C(Me)=NXy)(Cl)(1,2-bis(diphenylphosphino)ethane) | 476015-01-7

• 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: Pd(C(Me)=NXy)(Cl)(1,2-bis(diphenylphosphino)ethane)
• 英文别名: [Pd(C(CH3)=NXyl)Cl(dppe)]；chloropalladium(1+);N-(2,6-dimethylphenyl)ethanimine;2-diphenylphosphanylethyl(diphenyl)phosphane
• CAS: 476015-01-7
• 化学式: C₃₆H₃₆ClNP₂Pd
• 分子量: 686.509
• InChiKey: GWTOUDDICUFFSV-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：

  Pd(C(Me)=NXy)(Cl)(1,2-bis(diphenylphosphino)ethane) 以 乙醚 、 二氯甲烷 为溶剂， 生成 [Pd(C(Me)=NHXy)(Cl)(1,2-bis(diphenylphosphino)ethane)(phenyl isothiocyanate)][BF4]2
  参考文献：
  名称：

  Studies on the Reactivity of Isocyanates and Isothiocyanates with Palladium−Imidoyl Complexes

  摘要：

  The reactions of palladium-iminoacyl complexes with isocyanates (RNCO) and isothiocyanates (RNCS) have been investigated. The reaction of Pd{C(Me)=NXy}(Cl)(P-P) (P-P = dppe, 1; dppp, 2) with RNCE (E = O, S) in the presence of AgBF4 yields the novel compounds [Pd{C(=CH2)N(Xy)C(=E)NHR}(dppe)][BF4] (E = O and R = Et, 3; Ph, 4; E = S and R = Me, 5; Ph, 6); the formation of these complexes results from an addition reaction followed by the migration of a proton from the methyl group in the imidoyl fragment to the nitrogen in the RNCE moiety. In contrast, the reaction between Pd{C(Ph)=NXy}(I)(dppe) and RNCO in the presence of AgBF4 yields the addition product [Pd{C(Ph)=N(Xy)C(=O)(= NPh)}(dppe)]-[BF4] (10). Protonation of the imidoyl group in Pd{C(Me)=NXy}(Cl)(dppe) suppresses the addition reaction when the protonated complex is reacted with RNCS; the products obtained in this case are [Pd{C(Me)=NHXy}(dppe)(S=C=NR)] [BF4](2) (R = Me, 15; Ph, 16).

  DOI：

  10.1021/om030493r
• 作为产物：
  描述：

  [1,1'-bis(diphenylphosphino)ethane(Pd(CH3)Cl)] 、 2,6-二甲基苯基异腈 以 四氢呋喃 为溶剂， 以83%的产率得到Pd(C(Me)=NXy)(Cl)(1,2-bis(diphenylphosphino)ethane)
  参考文献：
  名称：

  Influence of Chelating Phosphines on the Insertion of Isocyanides into Palladium−Methyl Bonds in (P−P)Pd(Me)Cl Complexes and Their Further Reaction with Olefins and Isothiocyanates

  摘要：

  A systematic study of the insertion reactions between (P-P)Pd(Me)Cl (where P-P = dppe, dppp, dppf) and CNR (where R = 2,6-dimethylphenyl, tert-butyl) is presented. The results have demonstrated that the insertion of CNR into the Pd-Me bond is highly dependent on the nature of the chelating phosphine. For the more strained complex formed with dppe, the insertion of isocyanides is slower and multiple insertion is not observed. This is in contrast to (dppp)Pd(Me)Cl, which reacts readily with isocyanides to produce single-, double-, and multiple-inserted products. Results analogous to those of dppp have been observed for the complexes with dppf, although the reactions are more controllable, indicating a less reactive complex. In an attempt to establish some structure-reactivity correlations, structural characterizations of (dppe)Pd{C(Me)=NXyl}Cl (1) and (dppp)Pd{(C=NXyl)(C(Me)=NXyl)}-Cl (3) have been carried out. The structural parameters obtained are consistent with the observed reactivity. The reactions between (dppe)Pd{C(Me)=NXyl}Cl and unsaturated (olefins and isothiocyanates) species have also been studied. While norbornadiene (a strained diolefin) inserts into the palladium-iminoacyl bond, an addition is observed when reacting 1 with isothiocyanates.

  DOI：

  10.1021/om020444z

文献信息

• Palladium Iminoacyl Imine Complexes: Strategies toward Imine Insertion
  作者：Gareth R. Owen、Andrew J. P. White、Ramon Vilar

  DOI：10.1021/om900574b

  日期：2009.10.12

  The syntheses and characterization of a number of palladium complexes containing imine and/or iminoacyl groups are reported. Our strategies toward the insertion of imines into palladium iminoacyl complexes are outlined. The imine complexes [Pd(Me)(L-2)N(R')=C(H)Ph}]X (where L-2 = dppe, dppp, dppf, R' = Ph, Me, Bz; and X = BF4 or OTf) were prepared and fully characterized. [Pd(Me)(dppe)N(Ph)=C(H)Ph}]BF4 (1) and [Pd(Me)(dppp)N(Ph)=C(H)Ph}]OTf (4) were structurally characterized by X-ray crystallography. The iminoacyl-imine complexes [PdC(Me)=NXyl} (L-2)N=C(Me)OCH2CH2}]BF4 (L-2 = dppe, 12; dppp, 13) were prepared. The bis-imine complex [Pd(dppe)N=C(Me)OCH2CH2}][BF4](2) (14) resulting from disproportionation of 12 was also prepared and structurally characterized. Protonation of the iminoacyl fragment provided iminoacyl imine complex [PdC(CH3)=N(H)Xyl}(dppe)N(Bz)=CPhH}][BF4](2) (17), which was sufficiently stable to be structurally characterized, providing some insight into the coordination of these fragments of palladium.