dichloro((P,P)-1,1-bis(di(o-N,N-dimethylanilinyl)phosphino)methane)palladium(II) | 725719-43-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: dichloro((P,P)-1,1-bis(di(o-N,N-dimethylanilinyl)phosphino)methane)palladium(II)
• 英文别名: PdCl2(P,P'-1,1-bis[di(o-N,N-dimethylanilinyl)phosphino]methane)；PdCl2(1,1-bis(di(o-N,N-dimethylanilinyl)phosphino)methane)；2-[bis[2-(dimethylamino)phenyl]phosphanylmethyl-[2-(dimethylamino)phenyl]phosphanyl]-N,N-dimethylaniline;palladium(2+);dichloride
• CAS: 725719-43-7
• 化学式: C₃₃H₄₂Cl₂N₄P₂Pd
• 分子量: 733.997
• InChiKey: BNTWFPPUVJJPQI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -0.52
• 重原子数：
  42
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 dichloro((P,P)-1,1-bis(di(o-N,N-dimethylanilinyl)phosphino)methane)palladium(II) 以 二氯甲烷 、 丙酮 为溶剂， 以61%的产率得到[Pd(μ-Cl)(P,P'-1,1-bis(di(o-N,N-dimethylanilinyl)phosphino)methane)]2[PF6]2
  参考文献：
  名称：

  带有oN，N-二甲基苯胺基取代基的双膦配体的铂（II）和钯（II）配合物：催化烯烃水合的提示。

  摘要：

  潜在的六齿P，N供体配体家族Ar2P-X-PAr2（X =（CH2）2 [dmape]，环状C5H8 [dmapcp]; Ar = oN，N-描述了二甲基苯胺基。在CH2Cl2中，dmape络合物以MCl2（P，P'-dmape）和[MCl（P，P'，N-dmape）] Cl异构体（M = Pd，Pt）的平衡混合物形式存在，由deltaH（o）决定= -19 +/- 4 kJ mol（-1）和deltaS（o）= -100 +/- 30 J mol（-1）K（-1）对于M = Pt和deltaH（o）= -11 + /-7 kJ mol（-1）和deltaS（o）= -60 +/- 20 J mol（-1）K（-1）对于M = Pd。水溶性dmapcp配合物仅以[MC1（P，P'，N-dmapcp）] Cl形式存在，但这些配合物中的游离和配位苯胺基环处于缓慢的非对映选择性交换状态。MCl2（P，P'-dmape）（M

  DOI：

  10.1021/ic048639h
• 作为产物：
  描述：

  1,1-bis(di(o-N,N-dimethylanilinyl)phosphino)methane 、 bis(benzonitrile)palladium(II) chloride 以 二氯甲烷 为溶剂， 生成 dichloro((P,P)-1,1-bis(di(o-N,N-dimethylanilinyl)phosphino)methane)palladium(II) 、 dichloro((P,P)-1,1-bis(di(o-N,N-dimethylanilinyl)phosphino)methane)palladium(II)
  参考文献：
  名称：

  Metal−Metal Bonded Homo- and Heterobimetallic Compounds of Pt(I) and Pd(I) Supported by a Bridging-N,P:N‘,P‘ Moiety of a Potentially Hexadentate Ligand

  摘要：

  Reactions of metal-metal bonded homobimetallic (Pd-2) and heterobimetallic (PtPd) complexes, supported by a P,P'-bridging-bis(P,N-chelating) coordination mode of the potentially hexadentate ligand 1,1-bis[di(o-N,N-dimethylanilinyl)phosphino]methane (dmapm), with CO, diethylacetylenedicarboxylate (DEAD), and thiols (FISH) in CH2Cl2 are described. At room temperature, rac-Pd2Cl2(mu-N,P:P',N'-dmapm) gives the stable complexes Pd2Cl2(mu-CO)(2)-(mu-P:P'-dmapm) and PdCl(eta(2)-DEAD)(mu-P:P', N-dmapm)PdCl (which is fluxional in solution), while rac-PtPdCl2(mu-N,P:P', N'-dmapm) disproportionates to PtCl2(P,P'-dmapm) and Pd metal, although at low temperature intermediate carbonyl species are detected in the CO reaction. The reactions with thiols in the presence of triflic acid (HOTf) generate rac-[MPdCl2(mu-SR)(mu-N,P:P',N'-dmapm)][OTf] and H-2 for both M = Pt and Pd. In CH2Cl2, PdX2(dmapm) species (X = halide or CN) exist as equilibrium mixtures of P,P' and P,N-ligated forms. For X = Cl, the P,P'-PN equilibrium is governed by DeltaHdegrees = -5.5 +/- 0.5 kJ mol(-1) and DeltaSdegrees = 10 +/- 1 J mol(-1) K-1, and the ring-strain energy within the P,P'-isomer is similar to32 kJ mol(-1); the equilibrium increasingly favors the P,N-form with X = CN much greater than I > Br > Cl. The solid-state structures of rac-[PtPdCl2(mu-SEt)(mu-NP:P',N'-dmapm)][OTf] and PdCl2(P,N-dmapm) are presented; the latter contains both bound and free N- and P-atoms of identical types in the same molecule and permits an assessment of sigma- and pi-bonding between these atoms and Pd.

  DOI：

  10.1021/ic040019t

文献信息

• Palladium(II) complexes of bis(phosphine)monooxide and bis(phosphine)monosulphide ligands bearing <i>o</i>-<i>N</i>,<i>N</i>-dimethylanilinyl substituents
  作者：Nathan D Jones、Brian R James

  DOI：10.1139/v05-067

  日期：2005.6.1

  Palladium(II) complexes of bis(phosphine)monooxide and bis(phosphine)monosulphide ligands with the general formula Ar2P(CH2)nP(E)Ar2 are described (n = 1 (dmapmE), E = O, S; n = 2 (dmapeE), E = O; Ar = o-N,N-dimethylanilinyl). The precursor, PdCl2(dmapm), which exists in solution as an equilibrium mixture of the P,P- and P,N-ligated isomers, reacts with peroxides to form PdCl2(P,N-dmapmO) and with

  描述了具有通式 Ar2P(CH2)nP(E)Ar2 的双 (膦) 单氧化物和双 (膦) 单硫化物配体的钯 (II) 配合物 (n = 1 (dmapmE), E = O, S; n = 2 (dmapeE)，E = O；Ar = oN,N-二甲基苯胺基)。前体 PdCl2(dmapm) 作为 P,P- 和 P,N-连接异构体的平衡混合物存在于溶液中，与过氧化物反应形成 PdCl2(P,N-dmapmO) 并与硫反应生成 [PdCl (P,N,S-dmapmS)]Cl，可能是通过直接氧化 P,N 异构体的“悬空”P 原子。PdCl2(dmape) 以 PdCl2(P,P-dmape) 和 [PdCl(P,P,N-dmape)]Cl 的混合物形式存在于溶液中，在氩气下与 H2O?? Cl2 中的氢氧化物反应得到表面含有阳离子 [Pd2Cl2(μ-P,N:O-dmapeO)2]2+ 的 -to-face