chloro(4,4'-di-tert-butyl-2,2'-bipyridine)methylpalladium(II) | 524936-75-2

• 英文名称: chloro(4,4'-di-tert-butyl-2,2'-bipyridine)methylpalladium(II)
• 英文别名: (4,4′-di-tert-butyl-2,2′-bipyridine)PdMeCl；(^tBu₂bipy)PdMeCl；Pd(CH3)(Cl)(4,4'-di-tert-butyl-2,2'-dipyridyl)；[(4,4'-di-tert-butyl-2,2'-bipyridine)Pd(Me)Cl]；(4,4'-di-tert-butyl-2,2'-bipyridine)PdMeCl；[PdMeCl(4,4'-(t-Bu)2-2,2'-bipyridine)]
• CAS: 524936-75-2
• 化学式: C₁₉H₂₇ClN₂Pd
• 分子量: 425.31
• InChiKey: HUDZFGDGSDCSEQ-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：

  chloro(4,4'-di-tert-butyl-2,2'-bipyridine)methylpalladium(II) 以 二氯甲烷-D2 为溶剂， 生成 [(4,4'-di-tert-butyl-2,2'-bipyridine)Pd(Me)(CO)][B(C6F5)4]
  参考文献：
  名称：

  Reaction of Vinyl Chloride with Cationic Palladium Acyl Complexes

  摘要：

  Vinyl chloride (VC) reacts with the cationic Pd complexes [L2Pd(Me)(CO)] [B(C6F5)(4)] (3a-d; L-2 = Me(2)bipy, (t)Bu(2)bipy, dppp, dmpe) and [L2Pd{C(=O)Mej(CO)] [B(C6F5)(4)] (4a-d) by 2,1-insertion of L2Pd{C=O)Me}(VC)(+) intermediates to yield the O-chelated products [L2Pd-CHClCH2C(=O)Me}[B(C6F5)(4)] (5a-d). 5a-d were characterized by NMR spectroscopy, and the molecular structures of 5a and 5b.CH2Cl2 were determined by X-ray crystallography. The VC 2,1-insertion regiochemistry is favored in part because the alternative L2Pd{CH2CHClC(=O)Me}(+) 1,2-insertion products would be destabilized by placement of the electron-withdrawing Cl and acyl substituents on the same carbon. In contrast to analogous nonhalogenated L2Pd{CHRCHR'C(=O)Me}(+) species, 5a,c do not further react with CO, due to the stability of the chelate ring and the low migratory aptitude of the -CHClCH2C(=O)Me group.

  DOI：

  10.1021/om021028h
• 作为产物：
  描述：

  dichloro(4,4'-di-tert-butyl-2,2'-bipyridine)palladium(II) 、 (4,4'-di-tert-butyl-2,2'-bipyridine)dimethylpalladium(II) 以 acetone-d6 为溶剂， 生成 chloro(4,4'-di-tert-butyl-2,2'-bipyridine)methylpalladium(II)
  参考文献：
  名称：

  钯（II）中心之间甲基交换的计算和实验研究

  摘要：

  2当量的歧化（L）2加入Pd（CH 3）（X）以形成1个当量的（L）2加入Pd（CH 3）2（L）和1当量2的Pd（X）2可作为甲烷催化氧化低聚的关键步骤。使用DFT计算，已评估了与该转变有关的热力学与支撑配体L和X的关系。以这些计算为指导，我们展示了使用（t Bu-bpy）Pd（CH 3）（CH 2）的Pd II单甲基配合物歧化生成Pd II二甲基物种的第一个实验示例。COCH 3）（吨卜联吡啶= 4,4'-二-叔丁基-2,2'-联吡啶）作为起始原料。

  DOI：

  10.1021/om901039u

文献信息

• Reductive Elimination from Metal Phosphonate Complexes:  Circumvention of Competing Protonolysis Reactions
  作者：Robert A. Stockland,、Adam M. Levine、Matthew T. Giovine、Ilia A. Guzei、Joseph C. Cannistra

  DOI：10.1021/om0342309

  日期：2004.2.1

  phosphines. Analogous complexes bearing large bite angle diphosphines such as dppf and Xantphos undergo reductive elimination at ambient temperature. The rate of MeP(O)(OPh)2 formation by reductive elimination from (dppf)PdMe(P(O)(OPh)2) is not affected by the identity or concentration of added ligand (excess dppf or PPh3), suggesting that the reductive elimination occurs from a four- or three-coordinate

  已经研究了通过还原消除L 2 PdMe（P（O）（OPh）2）物种形成MeP（O）（OPh）2的方法。通过研究一系列含有氮和磷基配体的离散配合物的还原消除反应，研究了支持配体的电子和空间效应。当中间物种包含双齿氮配体或小的碱性单齿膦时，P（O）-C（sp 3）键形成反应缓慢。带有大咬角二膦的类似配合物（例如dppf和Xantphos）在环境温度下会进行还原消除。通过（dppf）PdMe（P（O）（OPh）2的还原消除形成MeP（O）（OPh）2的速率）不受添加配体（过量dppf或PPh 3）的身份或浓度的影响，表明还原消除是从四坐标或三坐标中间体发生的。当还原消除的速度很慢时，L 2 PdMe（P（O）（OPh）2）中间体和HP（O）（OPh）2之间的质子分解反应会导致双膦酸酯复合物的形成。质子分解反应可以通过使用较大的咬角磷化氢来避免，例如dppf和Xantphos，这会导致P（O）-C（sp
• Acrylonitrile Insertion Reactions of Cationic Palladium Alkyl Complexes
  作者：Fan Wu、Stephen R. Foley、Christopher T. Burns、Richard F. Jordan

  DOI：10.1021/ja044122t

  日期：2005.2.1

  with "L(2)PdMe+" species were investigated; (L(2) = CH(2)(N-Me-imidazol-2-yl)(2) (a, bim), (p-tolyl)(3)CCH(N-Me-imidazol-2-yl)(2) (b, Tbim), CH(2)(5-Me-2-pyridyl)(2) (c, CH(2)py'(2)), 4,4'-Me(2)-2,2'-bipyridine (d), 4,4'-(t)Bu(2)-2,2'-bipyridine (e), (2,6-(i)Pr(2)-C(6)H(3))N=CMeCMe=N(2,6-(i)Pr(2)-C(6)H(3)) (f)). [L(2)PdMe(NMe(2)Ph)][B(C(6)F(5))(4)] (2a-c) and [L(2)PdMe}(2)(mu-Cl)][B(C(6)F(5))(4)] (2d-f)

  研究了丙烯腈 (AN) 与“L(2)PdMe+”物质的反应；(L(2) = CH(2)(N-Me-imidazol-2-yl)(2) (a, bim), (p-tolyl)(3)CCH(N-Me-imidazol-2-yl) (2) (b, Tbim), CH(2)(5-Me-2-吡啶基)(2) (c, CH(2)py'(2)), 4,4'-Me(2)-2 ,2'-联吡啶 (d), 4,4'-(t)Bu(2)-2,2'-联吡啶 (e), (2,6-(i)Pr(2)-C(6)H) (3))N=CMeCMe=N(2,6-(i)Pr(2)-C(6)H(3)) (f))。[L(2)PdMe(NMe(2)Ph)][B(C(6)F(5))(4)] (2a-c) 和 [L(2)PdMe}(2)(mu- Cl)][B(C(6)F(5))(4)] (2d-f) 与 AN 反应形成 N 键合加合物 L(2)Pd(Me)(NCCH=CH(2))(
• Arylpalladium Phosphonate Complexes as Reactive Intermediates in Phosphorus−Carbon Bond Forming Reactions
  作者：Mark C. Kohler、Thomas V. Grimes、Xiaoping Wang、Thomas R. Cundari、Robert A. Stockland

  DOI：10.1021/om800906m

  日期：2009.2.23

  reactions, palladium complexes containing electron-donating substituents on the aromatic fragment exhibited faster rates of reductive elimination. Large bite angle diphosphine ligands induced rapid rates of elimination, while bipyridine and small bite angle diphosphine ligands resulted in much slower rates of elimination. An investigation of the effect of typical impurities on the elimination reaction

  由离散的过渡金属络合物形成的磷-碳键已通过合成，光谱，晶体学和计算方法的组合进行了研究。（二膦）Pd（芳基）（P（O）（OEt）2类型的反应性中间体）已经被制备，表征和研究为金属介导的偶联反应中的可能中间体。几种反应性中间体在晶体学上进行了表征，并对固态结构进行了讨论。与其他碳-杂原子键形成反应相反，在芳族片段上包含给电子取代基的钯配合物表现出更快的还原消除速率。大咬合角二膦配体诱导快速消除，而联吡啶和小咬合角二膦配体导致缓慢得多的消除。研究了典型杂质对消除反应的影响。虽然过量的二膦，吡啶和乙腈对观察到的速率影响很小，加水减慢了磷碳键的形成反应。在光谱和晶体学上观察到水与配合物的配位。计算研究被用来探测通过Pd催化形成Pc键的反应途径。
• Synthesis and Structural Characterization of a Novel Dipalladium Complex with an Unprecedented PdCN Bonding Motif
  作者：Gareth R. Owen、Ramón Vilar、Andrew J. P. White、David J. Williams

  DOI：10.1021/om030235u

  日期：2003.7.1

  Removal of the chloride atom from PdC-(=NXy)CH3}(Cl)(Bu(2)(t)bipy) initiates a series of reactions that lead to the formation of the novel dipalladium complex [Pd(Bu(2)(t)bipy) eta(2)-[pd(Bu(2)(t)bipy) N(Xy)=C(CH3)-C(CH3)=NXy}]}][BF4](2). In this process, two imidoyl groups undergo a C-C coupling reaction generating a bis-imino ligand that coordinates to two palladium centers, one of which is bound to a C-N bond of the ligand giving an unprecedented three-membered PdCN ring.