Pd(CNC6H4-p-CF3)2Cl2 | 950743-49-4

• 英文名称: Pd(CNC6H4-p-CF3)2Cl2
• 英文别名: cis-dichloridobis(p-trifluoromethylpenylisocyanide)palladium(II)；cis-dichlorobis(p-trifluoromethylphenylisocyanide)palladium(II)；Pd(CNC₆H₄-p-CF₃)₂Cl₂；bis(p-CF3-C6H4NC)palladium(II) dichloride
• CAS: 950743-49-4
• 化学式: C₁₆H₈Cl₂F₆N₂Pd
• 分子量: 519.569
• InChiKey: RWSKZCLMDXYHNR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  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(CNC6H4-p-CF3)2Cl2 、 N,N'-bis[1-(1-naphthyl)ethyl]-1,3-diaminopropane 以 乙腈 为溶剂， 以20%的产率得到(CH2)3(NCH(C10H7)CH3CNHC6H4CF3)2 palladium dichloride
  参考文献：
  名称：

  双（无环二氨基碳烯）配体与手性N-取代基和8元螯合环的钯配合物

  摘要：

  的反应顺-dichloridobis（p -trifluoromethylphenylisocyanide）钯（II）与Ñ，Ñ ' -双[（[R）-1-苯乙基] -1,3-二氨基丙烷，得到对映体纯，c ^ 1 -对称双（无环diaminocarbene） PdCl 2络合物的产率为41％。该配合物的X射线晶体结构表明，四个卡宾氮中的三个被扭出了与卡宾单元的共轭，这显然是由于一个苯基与螯合物的丙烯主链之间的空间相互作用所致。用类似的反应Ñ，Ñ ' -双[（ř）-1-（1-萘基乙基）-1,3-二氨基丙烷不会生成可分离的双（卡宾）络合物，而是形成大量的双（铵）盐作为分解产物。然而，相同的钯异氰化物前体与N，N'-双[1-（1-（萘基）乙基] -1,3-二氨基丙烷的所有非对映异构体的混合物的反应提供了一个非手性，C s-对称的钯双（无环）二氨基卡宾）络合物仅由（R，S）二胺衍生而来，产率为20％。

  DOI：

  10.1016/j.jorganchem.2009.06.007
• 作为产物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 1-异氰基-4-三氟甲基苯 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 Pd(CNC6H4-p-CF3)2Cl2
  参考文献：
  名称：

  Interplay of Metallophilic Interactions, π–π Stacking, and Ligand Substituent Effects in the Structures and Luminescence Properties of Neutral Pt^II and Pd^II Aryl Isocyanide Complexes

  摘要：

  Packing interactions in the crystal structures of a series of cis-M(CNAr)(2)Cl-2 complexes (M = Pt, Pd; Ar = substituted phenyl) were examined and correlated with the luminescence properties of the Pt complexes. The structures of the PhNC and p-tolyl isocyanide complexes exhibit extended chains of metallophilic interactions with M center dot center dot center dot M distances of 3.24-3.25 and 3.34 angstrom, respectively, with nearly isostructural Pt and Pd compounds. Both structure types contain void channels running parallel to the M center dot center dot center dot M chains. The channels are 3-4 angstrom wide and vacant for the phenyl structures, while those in the p-tolyl structures are up to 7.6 angstrom wide and contain water. These channeled structures are stabilized by a combination of metallophilic bonding and aryl pi-pi stacking interactions. The Pt structure with 4-F substituents also features extended Pt center dot center dot center dot Pt chains, but with longer 3.79 angstrom distances alternating with shorter 3.37 angstrom contacts. Structures with 4-CF3 and 4-OMe substituents exhibit mostly isolated dimers of M center dot center dot center dot M contacts. In complexes with 2,6-dimethylphenyl isocyanide, steric hindrance precludes any short M center dot center dot center dot M contacts. The primary effect of aryl substitution is to provide alternative packing motifs, such as CF3 center dot center dot center dot pi and CH3 center dot center dot center dot pi interactions, that either augment or disrupt the combination of metallophilic contacts and pi-pi stacking needed to stabilize extended M center dot center dot center dot M chains. Differences in the Pt and Pd structures containing 4-F and 4-OMe substituents are consistent with a higher driving force for metallophilic interactions for Pt versus Pd. The M-C and M-Cl bond distances indicate a slightly higher trans influence for aryl isocyanides bound to Pt versus Pd. The three extended Pt center dot center dot center dot Pt chain structures display luminescence assignable to (d sigma*-p sigma) excited states, demonstrating the existence of substantial orbital communication along the metal-metal chains. Face-indexing shows that the preferred crystal growth axis is along the metal-metal chains for the luminescent structures. Variable temperature structural studies showed that both M center dot center dot center dot M and pi-pi interactions contract upon cooling. Overall, this study suggests that synergy with pi-pi and other interactions is necessary to stabilize extended M center dot center dot center dot M chain structures. Thus, efforts to design functional materials based on metallophilic bonding must consider the full array of available packing motifs.

  DOI：

  10.1021/ic301104a

文献信息

• Chiral Palladium Bis(acyclic diaminocarbene) Complexes as Enantioselective Catalysts for the Aza-Claisen Rearrangement
  作者：Yoshitha A. Wanniarachchi、Yuri Kogiso、LeGrande M. Slaughter

  DOI：10.1021/om701029j

  日期：2008.1.1

  Palladium complexes of chiral bis(acyclic diaminocarbene) ligands with seven-membered chelate rings catalyze the aza-Claisen rearrangement of an allylic benzimidate to an allylic amide with moderate yields and enantioselectivities of 30–59% ee. The promotion of electrophilic catalysis by complexes of these ligands highlights their distinct stereoelectronic properties relative to those of common bis(N-heterocyclic

  具有七元螯合环的手性双（无环二氨基碳烯）配体的​​钯配合物可催化将烯丙基苯丙二酸酯的氮杂-克莱森重排成烯丙基酰胺，且产率适中，对映选择性为30-59％ee。这些配体的配合物对亲电子催化的促进突出了其相对于普通双（N-杂环卡宾）的独特的立体电子性质。
• One-step assembly of a chiral palladium bis(acyclic diaminocarbene) complex and its unexpected oxidation to a bis(amidine) complex
  作者：Yoshitha A. Wanniarachchi、LeGrande M. Slaughter

  DOI：10.1039/b703769d

  日期：——

  Addition of trans-N,N'-dimethyl-1,2-diaminocyclohexane to a palladium bis(arylisocyanide) complex leads to the one-step formation of the first chiral bis(acyclic diaminocarbene) complex, which is thermally stable under N(2) but undergoes slow oxidation to a bis(amidine) complex under air.

  将反式N，N'-二甲基-1,2-二氨基环己烷添加到钯双（芳基异氰化物）配合物中可一步形成第一手性双（无环二氨基碳烯）配合物，该配合物在N（2）下是热稳定的），但在空气中缓慢氧化成双（am）络合物。
• Reversible Chelate Ring Opening of a Sterically Crowded Palladium Bis(acyclic diaminocarbene) Complex
  作者：Yoshitha A. Wanniarachchi、LeGrande M. Slaughter

  DOI：10.1021/om700866p

  日期：2008.3.24

  Reaction of cis-dichlorobis(p-trifluoromethylphenylisocyanide)palladium(II) with hydrazobenzene afforded a complex with a monodentate aminohydrazino carbene ligand and an unreacted arylisocyanide. Upon heating, this complex partially converted into a chelating bis(acyclic diaminocarbene) complex. Both the monocarbene and bis(carbene) complexes were isolated and characterized by X-ray crystallography. In solution, an equilibrium between the monocarbene and bis(carbene) complexes was observed, with equilibrium constants of 2.56(15) in CD3CN and 10.0(5) in THF-d(8) at 25 degrees C. A van't Hoff plot provided thermodynamic parameters of Delta H degrees = -1.7(3) kcal mol(-1) and Delta s degrees = -3.7(9) eu for the monocarbene to bis(carbene) conversion in CD3CN. The instability of the bis(carbene) complex toward chelate ring opening was rationalized on the basis of steric strain apparent in the X-ray structure. The crowded syn,syn arrangement of aryl groups on the bis(carbene) backbone results in widening of the carbene NCN angles to reduce aryl-aryl steric interactions. Thermodynamic calculations on density functional theory models of the carbene complexes were in reasonable agreement with experimental data, and they provided ail estimate of 16 kcal mol(-1) for the maximum amount of ligand strain that can be accommodated in forming a stable bis(carbene) ligand via diamine addition to cis isocyanides. The chelating bis(carbene) is thermodynamically favored despite an unfavorable reaction entropy and a substantial amount of ligand strain.