[Pd(acetonitrile)2(C4(COOCH3)4)] | 827019-73-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: [Pd(acetonitrile)2(C4(COOCH3)4)]
• 英文别名: [Pd(C4(COOMe)4)(acetonitrile)2]；[Pd(C4(COOMe)4)(CH3CN)2]
• CAS: 827019-73-8
• 化学式: C₁₆H₁₈N₂O₈Pd
• 分子量: 472.748
• InChiKey: OJQPARFJJGQVBC-UHFFFAOYSA-N

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(acetonitrile)2(C4(COOCH3)4)] 、 1,3-双(2,4,6-三甲基苯基)氯化咪唑 在 NaH 作用下， 以 not given 为溶剂， 生成 [Pd(acetonitrile)(C4(COOMe)4)(1,3-bis(mesityl)imidazol-2-ylidene)]
  参考文献：
  名称：

  Pd(NHC)-催化炔烃转移氢化的机理

  摘要：

  当使用零价钯 (NHC)（马来酸酐）-配合物作为预催化剂和甲酸三乙基铵作为氢供体时，炔烃向 (Z)-烯烃的转移半氢化显示出优异的化学和立体选择性。对反应条件下动力学的研究表明，底物正序和催化剂和氢供体的一级顺序被破坏。对氢供体的氘标记研究表明，甲酸的两个氢都显示出主要的动力学同位素效应，表明质子和氢化物转移是单独的速率决定步骤。通过用 NMR 监测反应，我们观察到配位甲酸阴离子的存在，并发现部分马来酸酐在反应过程中保持配位。从这些观察中，我们提出了一种机制，其中氢从配位甲酸阴离子转移到零价钯（NHC）（MA）（炔）-络合物，随后是氢化物的迁移插入，之后产物烯烃通过从三乙基铵阳离子的质子转移释放。观察到的高选择性的解释在于强配位溶剂和炔烃之间对 Pd（烯烃）-中间体的竞争。

  DOI：

  10.1021/ja1062407
• 作为产物：
  描述：

  乙腈 、 [1,2,3,4-tetrakis(methoxycarbonyl)1,3-butadiene-1,4-diyl]palladium 以 乙腈 为溶剂， 以85%的产率得到[Pd(acetonitrile)2(C4(COOCH3)4)]
  参考文献：
  名称：

  New palladacyclic complexes with pyridylphosphine ligands: crystal structures of [Pd(Azb)(Ph2POCH2Py-P,N)][PF6] and [Pd(Phpy)(Ph2PNHPy-P,N)][PF6]

  摘要：

  The synthesis of palladacyclic derivatives with the hybrid pyridylphosphine ligands Py(CH2)OPPh2 (a) and PyNHPPh2 (b) in a neutral P,N-chelating coordination mode has been achieved. Treatment of selected chloride-bridged cyclometallated precursors [Pd((CN)-N-boolean AND)(mu-Cl)](2) [(CN)-N-boolean AND=2-pyridinin-phenyl Phpy, I-compounds; 7,8-benzoquinolyl Bzq, II-compounds; phenylazophenyl Azb, III-compounds or 2-(2-oxazolinyl)phenyl Phox, IV-compounds] with a or b in the presence of stoichiometric KPF6 gave the mononuclear derivatives Ia-IVa and Ib-IVb. The crystal structures of compounds [Pd(Azb)(Ph2POCH2Py-P,N)][PF6] (IIIa) and [Pd(Phpy)(Ph2PNHPy-P,N)][PF6] (Ib) have been determined. The new palladacyclopentachene precursor [Pd{C4COOMe4}(CH3CN)(2)] (V) has been prepared starting from the polymeric complex [Pd{C4COOMe4}](n). Its usefulness in the preparation of new derivatives has been tested by means of the straightforward reaction with ligands (a) or (b) to give mononuclear compounds [Pd{C-4(COOMe)(4)}(Ph2POCH2Py-P,N)] (Va) and [Pd{C-4(COOMe)(4)}(Ph2PNHPy-P,N)] (Vb). The reactions of hydroxo-bridged precursors [Pd-2((CN)-N-boolean AND)(mu-OH)](2) or [Pd-2{C-4(COOMe)(4)}(2) (mu-OH)(2)][NBu4](2) with PyNHPPh2 afforded mononuclear complexes Ic-Vc (PyNPPh2 = c ligand) in which a less common anionic P,N-binding mode is forced as a result of ligand deprotonation. The new complexes were characterised by partial elemental analyses and spectroscopic methods (IR, FAB, H-1 and P-31{H-1} NMR). (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2004.06.040

文献信息

• Formation and coordination modes of the C4E4 moiety (E = COOMe) bound to two palladium(ii) moieties
  作者：Tetsuro Murahashi、Taketoshi Okuno、Kentaro Usui、Kohei Takase、Toshiaki Otani、Sensuke Ogoshi、Hideo Kurosawa

  DOI：10.1039/c0dt01169j

  日期：——

  The transmetallation of the palladacyclopentadiene complex PdC(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy) with the dicationic PdII complex [Pd(bipy)(CH3CN)2][BF4]2 afforded a terminally σ-palladated diene complex [Pd2μ-η1:η1-C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)2(CH3CN)2][BF4]2. It was revealed by X-ray crystallographic analysis that replacement of the acetonitrile ligands in a terminally σ-palladated diene complex with PPh3 ligands resulted in the conformation change of the σ-palladated diene moiety from skewed s-cis to planar s-trans. Treatment of a bis-triphenylphosphine dipalladium complex [Pd2(PPh3)2(CH3CN)4][PF6]2 with dimethoxyacetylene dicarboxylate (DMAD) (1 equiv.) in acetonitrile resulted in the insertion of DMAD to the Pd–Pd bond to afford [Pd2μ-η1:η1-C(COOMe)C(COOMe)}(PPh3)2(CH3CN)4][PF6]2. Addition of the second DMAD gave the ylide-type complex [Pd2μ-η2:η3-C(COOMe)C(COOMe)C(COOMe)C(COOMe)(PPh3)}(PPh3)2(CH3CN)3][PF6]2 of which the structure was determined by X-ray crystallographic analysis.

  将 PdC(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)与二阳离子 PdII 复合物[Pd(bipy)(CH3CN)2][BF4]2 进行反金属化，可得到末端为 σ-palladated 的二烯复合物[Pd2μ-η1：η1-C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)2(CH3CN)2][BF4]2。X 射线晶体学分析表明，用 PPh3 配体取代末端 σ-palladated 二烯配合物中的乙腈配体，可使 σ-palladated 二烯分子的构象从偏斜的 s-cis 转变为平面的 s-trans。将双三苯基膦二钯配合物 [Pd2(PPh3)2(CH3CN)4][PF6]2与二甲氧基乙炔二羧酸盐（DMAD）（1 equiv.在乙腈中加入二甲氧基乙炔二羧酸盐 (DMAD)（1 等份），DMAD 插入 Pd-Pd 键，得到 [Pd2μ-η1:η1-C(COOMe)C(COOMe)}(PPh3)2(CH3CN)4][PF6]2。加入第二个 DMAD 后，得到了[Pd2μ-η2:η3-C(COOMe)C(COOMe)C(COOMe)C(COOMe)(PPh3)}(PPh3)2(CH3CN)3][PF6]2 的矢量型复合物，其结构已通过 X 射线晶体分析法确定。