(N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamidato)(η1-acetonitrile)palladium(II) | 262273-58-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamidato)(η1-acetonitrile)palladium(II)
• 英文别名: (C5H3N-2,6-(C(O)NCH2CH2Ph)2)PdNCMe；[Pd(N,N'-bis(2-phenylethyl)-2,6-pyridinecarboxamide(-2H))(MeCN)]；acetonitrile;palladium(2+);2-phenylethyl-[6-(2-phenylethylazanidylcarbonyl)pyridine-2-carbonyl]azanide
• CAS: 262273-58-5
• 化学式: C₂₅H₂₄N₄O₂Pd
• 分子量: 518.911
• InChiKey: DKUQCZHVKHGKGP-UHFFFAOYSA-L

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：

  (N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamidato)(η1-acetonitrile)palladium(II) 以 二氯甲烷 为溶剂， 以99%的产率得到tetrakis(μ-[N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamidato])tetrapalladium(II)
  参考文献：
  名称：

  Architectural formation of a conjugated bimetallic Pd(ii) complex via oxidative complexation and a tetracyclic Pd(ii) complex via self-assembling complexationElectronic supplementary information: experimental section and crystallography. Figs. S1–6. See http://www.rsc.org/suppdata/cc/b2/b203726m/

  摘要：

  1,4- 苯二胺与钯(II)络合物[(L1)Pd(MeCN)](H2L1 = N. N′-双(2-苯基乙基)-2,6-吡啶二甲酰胺)原位氧化络合，在一锅反应中获得了共轭同种金属钯(II)络合物[(L1)Pd(qd)Pd(L1)](qd = 醌二胺)、N′-双（2-苯基乙基）-2,6-吡啶二甲酰胺）进行原位氧化复配，而在没有额外配体的情况下，[(L1)Pd(MeCN)]会转化为酰胺桥接的大环四聚体[Pd(L1)]4。

  DOI：

  10.1039/b203726m
• 作为产物：
  描述：

  tetrakis(μ-[N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamidato])tetrapalladium(II) 以 乙腈 为溶剂， 生成 (N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamidato)(η1-acetonitrile)palladium(II)
  参考文献：
  名称：

  Architectural formation of a conjugated bimetallic Pd(ii) complex via oxidative complexation and a tetracyclic Pd(ii) complex via self-assembling complexationElectronic supplementary information: experimental section and crystallography. Figs. S1–6. See http://www.rsc.org/suppdata/cc/b2/b203726m/

  摘要：

  1,4- 苯二胺与钯(II)络合物[(L1)Pd(MeCN)](H2L1 = N. N′-双(2-苯基乙基)-2,6-吡啶二甲酰胺)原位氧化络合，在一锅反应中获得了共轭同种金属钯(II)络合物[(L1)Pd(qd)Pd(L1)](qd = 醌二胺)、N′-双（2-苯基乙基）-2,6-吡啶二甲酰胺）进行原位氧化复配，而在没有额外配体的情况下，[(L1)Pd(MeCN)]会转化为酰胺桥接的大环四聚体[Pd(L1)]4。

  DOI：

  10.1039/b203726m
• 作为试剂：
  描述：

  在 (N,N'-bis(2-phenylethyl)-2,6-pyridinedicarboxamidato)(η1-acetonitrile)palladium(II) 、 magnesium methanolate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 19.0h， 以60%的产率得到
  参考文献：
  名称：

  由于车轮沿车轴平移，特定于基于Pd的轮烷复合物的连续催化反应。

  摘要：

  轮烷结构特定的钯催化的炔丙基或烯丙基氨基甲酸酯基团向恶唑烷酮部分的重排有效地进行。通过车轮沿轴的平移相继进行转换，从而提供了一种新颖的大环催化系统。

  DOI：

  10.1039/b917053g

文献信息

• Multimetallic Complex Composed of Redox-Active Bridging Quinonediimine Ligand
  作者：Toshiyuki Moriuchi、Xiuliang Shen、Kaori Saito、Seiji Bandoh、Toshikazu Hirao

  DOI：10.1246/bcsj.76.595

  日期：2003.3

  A π-conjugated quinonediimine ligand possessing two terminal redox-active ferrocenyl groups, N,N′-bis(4′-ferrocenylcarboxamide)phenyl}-1,4-benzoquinonediimine (Lox), was synthesized. The quinonediimine ligand Lox was reduced to Lred composed of the phenylenediamine moiety on treatment with hydrazine hydrate. The reaction of Lox with the palladium(II) complex 1 bearing the N,N′-bis(2-phenylethyl)-2,6-pyridinedicarboxamide ligand afforded the multimetallic complex 2. Variable temperature 1H NMR studies of 2 indicated the existence of syn and anti isomers, in which the anti isomer is enthalpically more favorable than the syn isomer in CD2Cl2 by 0.9 kcal mol−1, but entropically less favorable by 2.6 cal mol−1 K−1 from the van’t Hoff plot. The redox function of the quinonediimine moiety is modulated by complexation with 1. The complex 2 showed three separate redox waves, which are assignable to the successive one-electron reduction of the quinonediimine moiety and oxidation of the two terminal ferrocenyl groups. Chemical reduction of 2 in CH2Cl2 with [Co(Cp)2] resulted in the appearance of ESR signals with weak 105Pd coupling centered around g = 2.004. The unpaired electron appears to locate mostly on the quinonediimine moiety with some delocalization onto the palladium center.

  一种具有两个末端氧化还原活性二茂铁基团的π-共轭醌二亚胺配体--N,N′-双(4′-二茂铁甲酰胺)苯基}-1,4-苯醌二亚胺（Lox）被合成出来。醌二亚胺配体 Lox 经肼水合物处理后被还原成由苯二胺分子组成的 Lred。Lox 与带有 N,N′-双（2-苯基乙基）-2,6-吡啶二甲酰胺配体的钯（II）络合物 1 反应，得到多金属络合物 2。对 2 的变温 1H NMR 研究表明，其中存在同分异构体和反异构体，在 CD2Cl2 中，反异构体的焓值比同分异构体高 0.9 kcal mol-1，但从范特霍夫曲线图来看，熵值比同分异构体低 2.6 cal mol-1 K-1。醌二亚胺分子的氧化还原功能受与 1 的络合物的调节。络合物 2 显示出三个独立的氧化还原波，可归因于醌二亚胺分子的连续单电子还原和两个末端二茂铁基团的氧化。用[Co(Cp)2]在 CH2Cl2 中对 2 进行化学还原后，出现了以 g = 2.004 为中心的弱 105Pd 耦合 ESR 信号。未配对的电子似乎主要位于醌二亚胺分子上，但也有一些分散到钯中心上。
• Palladium Homobimetallic Complexes with Bridging π-Conjugated Ligands
  作者：Toshiyuki Moriuchi、Seiji Bandoh、Masayuki Kamikawa、Toshikazu Hirao

  DOI：10.1246/cl.2000.148

  日期：2000.2

  The palladium homobimetallic complexes 2a and 2b with a bridging π-conjugated molecule, N,N′-bis(4′-pyridylmethylidene)-1,4-phenylenediamine (L2a) and 2′-pyridyl derivative L2b, were respectively synthesized and characterized by X-ray crystal structure analysis and cyclic voltammetry. 1H-NMR of 2b indicates the five-coordinate geometry on the palladium center.

  分别合成了具有桥联 π 共轭分子 N,N'-双(4'-吡啶亚甲基)-1,4-苯二胺 (L2a) 和 2'-吡啶基衍生物 L2b 的钯同双金属配合物 2a 和 2b，并进行了表征： X射线晶体结构分析和循环伏安法。 2b的1H-NMR表明钯中心的五配位几何形状。
• A Novel Redox-Active Conjugated Palladium Homobimetallic Complex
  作者：Toshiyuki Moriuchi、Seiji Bandoh、Manabu Miyaishi、Toshikazu Hirao

  DOI：10.1002/1099-0682(200103)2001:3<651::aid-ejic651>3.0.co;2-6

  日期：2001.3

  favorable by 4.5 cal/mol from the van’t Hoff plot. The redox function of the quinone diimine moiety is modulated by complexation with the palladium complex 1. The conjugated complex 2 shows three separate redox waves assignable to the successive one-electron reduction of the quinone diimine moiety and one-electron oxidation process of the two terminal dimethylamino groups. Chemical reduction of 2 in THF

  π-共轭分子 N,N'-双(4'-二甲氨基苯基)-1,4-苯醌二亚胺 (L2) 结合到带有 N,N'-双 (2-苯乙基) 的钯 (II) 配合物 1 中-2,6-吡啶二甲酰胺配体，以提供具有氧化还原活性的共轭钯 (II) 均双金属配合物 2。 2 的 X 射线晶体结构测定表明，两个钯配合物单元通过醌二亚胺部分桥接形成 C2-具有反构型的对称 2:1 复合物，并且桥接 π 共轭间隔基部分沿几乎平行于 a 轴的直线排列，以在分子堆积中形成 π 共轭分子的柱。共轭配合物 2 的变温 1H NMR 研究表明，顺式构型比 CD2CL2 中的反构型在焓上更有利 1。0 kcal/mol，但从 van't Hoff 图中熵降低了 4.5 cal/mol。醌二亚胺部分的氧化还原功能通过与钯配合物 1 的络合来调节。共轭配合物 2 显示三个独立的氧化还原波，可归因于醌二亚胺部分的连续单电子还原和两端的单电子氧化过程二甲氨基。用
• A novel heterobimetallic complex composed of the imide-bridged [3]ferrocenophane and the tridentate palladium(II) complex
  作者：Toshiyuki Moriuchi、Seiji Bandoh、Yoko Miyaji、Toshikazu Hirao

  DOI：10.1016/s0022-328x(99)00748-2

  日期：2000.4

  The imide-bridged [3]ferrocenophane, 2-pyridyl-1,1′-ferrocenedicarboximide, served as a monodentate ligand to form the corresponding heterobimetallic complex 4 with the palladium(II) complex bearing the tridentate podand ligand, through displacement of the ancillary acetonitrile. The X-ray crystal-structure determination revealed that the pyridyl nitrogen of the ferrocenophane coordinates to the palladium

  酰亚胺桥连的[3]二茂铁酚，2-吡啶基-1,1'-二茂铁芳族酰亚胺，作为单齿配体，与相应的带有双齿配体配体的钯（II）配合物形成相应的异双金属配合物4，通过置换辅助分子乙腈。X射线晶体结构的测定表明，二茂铁碳烷的吡啶氮与钯中心配位，而二茂铁碳烷部分位于铜的配位平面以下。甚至在溶液中也认为存在这种结构，导致1个Cp质子的四个非等价宽信号H-NMR光谱，由于钯的配位平面的电子环境效应。在4的晶体堆积中，豆角部分的苯环与相邻分子的吡啶环之间观察到π-π堆积相互作用。
• Coordination properties towards palladium(II) of a tridentate dianionic ligand acting as a N- or a N,O-donor
  作者：Daniela Belli Dell’Amico、Fausto Calderazzo、Francesco Di Colo、Gianfranco Guglielmetti、Luca Labella、Fabio Marchetti

  DOI：10.1016/j.ica.2005.06.073

  日期：2006.1

  The new palladium(II) complex Pd[C5H3N-2,6-(CONPh)(2)](eta(1)-NCMe) (1), prepared from N,N'-diphenyl-2,6-pyridinedicarboxamide and Pd(OAC)(2) in acetonitrile, has been characterized via IR, H-1 NMR and single-crystal X-ray diffraction. In this compound the palladium centre is coordinated to three nitrogen donors of the anionic ligand and to the nitrogen atom of acetonitrile.Moreover, the already known Pd[C5H3N-2,6-(CONCH2CH2Ph)(2)](eta(1)-NCMe) (2) has been studied by H-1 NMR spectrometry and found to readily convert into the macrocyclic tetranuclear species 3, Pd[C5H3N-2,6-(CONCH2CH2Ph)(2)]}4 which has been isolated and characterized by IR, H-1 and C-13 H-1-(NMR)-N-13, H-1-C-13 HETCOR and mass spectrometry, as well as by single-crystal X-ray diffraction. In 3, of S-4 symmetry, each palladium atom is coordinated to the three nitrogen atoms of the anionic ligand, while the fourth coordination position is occupied by the amidato oxygen atom of an adjacent unit. This structure is apparently maintained in CDCl3 solution. The substitution reactions of acetonitrile in 2 with the ligands EEt2 (E = S, Se) afford Pd[C5H3N-2,6-(CONCH,CH,Ph)(2)](EEt2) (4, E = S; 5, E = Se); these products can also be obtained by the addition of EEt2 to 3, as shown by means of H-1- and, in the case of E = Se, Se-77H-1} NMR spectroscopy in CDCl3 solution. These results show that the Pd-O bonds of the tetranuclear species are readily broken by weakly coordinating ligands such as acetonitrile and diethylchalcogenides. Nevertheless, we are dealing with equilibrium reactions and, in some solvents, 3 can be obtained from 2, 4 or 5 being favoured by its low solubility. (c) 2005 Elsevier B.V. All rights reserved.