Pd(cyclooctadiene)(maleic anhydride) | 64537-35-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: Pd(cyclooctadiene)(maleic anhydride)
• 英文别名: [palladium(0)(η2-maleic anhydride)(COD)]；[Pd(η2-ma)(COD)]；(1Z,5Z)-cycloocta-1,5-diene;furan-2,5-dione;palladium
• CAS: 64537-35-5
• 化学式: C₁₂H₁₄O₃Pd
• 分子量: 312.661
• InChiKey: ZITIZYVRIDNKBA-GCOBPYNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Pd(cyclooctadiene)(maleic anhydride) 、 1,3,4,5-tetramethylimidazol-2-ylidene 以 四氢呋喃 为溶剂， 以86%的产率得到Pd(1,3,4,5-tetramethylimidazol-2-ylidene)(maleic anhydride)
  参考文献：
  名称：

  杂环卡宾的零价钯和镍配合物：有机卤化物的氧化加成，碳-碳偶联过程和Heck反应

  摘要：

  合成了含有1,3,4,5-四甲基咪唑-2-亚甲基配体（tmiy）的Pd的零价卡宾络合物。Pd（COD）（烯烃）（COD =环辛二烯）与亲核卡宾tmiy反应生成配合物Pd（tmiy）2（烯烃）（烯烃=马来酸酐（MAH）（2），四氰基乙烯（TCNE）（3）） 。配合物的光谱研究提供了卡宾配体几乎纯的供体性质的有力证据。将烃基卤化物和二卤化物底物氧化加成至2和3得到Pd II衍生物Pd（tmiy）2（Ph）I（4），Pd（tmiy）2 I 2（5），Pd（tmiy）2（4-硝基苯基）I（6）和Pd（tmiy）2 Br 2（7）。Ni（COD）2与tmiy的反应原位生成零价Ni络合物Ni（tmiy）2，有机卤化物的氧化添加产生Ni（tmiy）2（邻甲苯基）Br（8），Ni（t tmiy）2（Me）I（9）和Ni（tmiy）2 I 2（10）。配合物8和10的X射线晶体结构据报道，其揭示了与卡宾配体

  DOI：

  10.1021/om9809771

文献信息

• Novel syn oxidative addition of allylic halides to olefin complexes of palladium(0) and platinum(0)
  作者：Hideo Kurosawa、Hiroshi Kajimaru、Sensuke Ogoshi、Hiroto Yoneda、Kunio Miki、Nobutami Kasai、Shinji Murai、Isao Ikeda

  DOI：10.1021/ja00048a011

  日期：1992.10

  (1b) and 5-methyl-2-cyclohexenyl chloride (1c) to palladium(0)-olefin and platinum(0)-olefin complexes to give the corresponding (η 3 -allyl)palladium and -platinum complexes was examined as a function of solvent and olefin ligands. Novel syn addition (>90% selectivity) occurred in the reactions of the trans isomers of 1a-c with palladium complexes containing electron-withdrawing olefenic ligands (maleic

  5-(甲氧基羰基)-2-环己烯基氯 (1a) 和溴化物 (1b) 和 5-甲基-2-环己烯基氯 (1c) 氧化加成到钯 (0)-烯烃和铂 (0)-烯烃的立体化学作为溶剂和烯烃配体的函数，研究了生成相应的 (η 3 -烯丙基) 钯和 - 铂配合物的配合物。在 1a-c 的反式异构体与包含吸电子烯烃配体（马来酸酐、富马酸二甲酯、富马腈、二亚苄基丙酮）的钯配合物在苯、CH 2 Cl 2 中进行的反应中发生了新的顺式加成（>90% 选择性） , 或四氢呋喃
• The interaction between heteroditopic pyridine–nitrogen NHC with novel sulfur NHC ligands in palladium(0) derivatives: Synthesis and structural characterization of a bis-carbene palladium(0) olefin complex and formation in solution of an alkene–alkyne mixed intermediate as a consequence of the ligands hemilability
  作者：Luciano Canovese、Fabiano Visentin、Carlo Levi、Claudio Santo、Valerio Bertolasi

  DOI：10.1016/j.ica.2012.04.018

  日期：2012.7

  We have synthesized a new class of heteroditopic chelating ligands bearing the phenylthiomethyl group and variously substituted imidazole derivatives and the corresponding complexes [Pd(eta(2)-ma)(R-NHC-CH2-SPh) (ma = maleic anhydride; R = methyl, mesityl, di-i-propylphenyl). We have compared their chemical characteristics and reactivity with those of similar palladium(0) complexes bearing the R-NHC-CH2-Py ligands.The hemilability of the above-mentioned moieties is apparent when their palladium derivatives react with an excess of the same or different heteroditopic ligands. In these cases, we obtained complexes bearing maleic anhydride and two mono-coordinated heteroditopic ligands bound to the same metal center. However, at variance with the generally accepted opinion, precipitation of AgBr does not warrant the quantitative formation of the bis-heteroditopic Pd(0) derivative and in some cases, a reaction involving a heterogeneous equilibrium is observed.The reaction of the palladium(0) carbene-sulfur or carbene-nitrogen complexes with the alkyne dimethyl-2-butynedioate (dmbd) to give palladacyclometallate derivatives is not always warranted and formation of the intermediate [Pd(eta(2)-ma)(eta(2)-dmdb)(kappa(1)-Mes-NHC-CH2-SPh)] is detected only in one case.Finally, we have carried out a diffractometric study on the solid-state structures of two derivatives and in particular we describe the configurations of the complex [Pd(eta(2)-ma)(kappa(1)-Me-NHC-CH2-SPh)(2)] and of [Pd(eta(2)-ma)(Me-NHC-CH2-SPh)]. (C) 2012 Elsevier B.V. All rights reserved.
• Zerovalent Palladium and Nickel Complexes of Heterocyclic Carbenes:  Oxidative Addition of Organic Halides, Carbon−Carbon Coupling Processes, and the Heck Reaction
  作者：David S. McGuinness、Kingsley J. Cavell、Brian W. Skelton、Allan H. White

  DOI：10.1021/om9809771

  日期：1999.4.1

  purely donor nature of the carbene ligand. Oxidative addition of hydrocarbyl halide and dihalide substrates to 2 and 3 yield the PdII derivatives Pd(tmiy)2(Ph)I (4), Pd(tmiy)2I2 (5), Pd(tmiy)2(4-nitrophenyl)I (6), and Pd(tmiy)2Br2 (7). The zerovalent Ni complex Ni(tmiy)2 was produced in situ from the reaction of Ni(COD)2 with tmiy, and the oxidative addition of organic halides yields Ni(tmiy)2(o-tolyl)Br

  合成了含有1,3,4,5-四甲基咪唑-2-亚甲基配体（tmiy）的Pd的零价卡宾络合物。Pd（COD）（烯烃）（COD =环辛二烯）与亲核卡宾tmiy反应生成配合物Pd（tmiy）2（烯烃）（烯烃=马来酸酐（MAH）（2），四氰基乙烯（TCNE）（3）） 。配合物的光谱研究提供了卡宾配体几乎纯的供体性质的有力证据。将烃基卤化物和二卤化物底物氧化加成至2和3得到Pd II衍生物Pd（tmiy）2（Ph）I（4），Pd（tmiy）2 I 2（5），Pd（tmiy）2（4-硝基苯基）I（6）和Pd（tmiy）2 Br 2（7）。Ni（COD）2与tmiy的反应原位生成零价Ni络合物Ni（tmiy）2，有机卤化物的氧化添加产生Ni（tmiy）2（邻甲苯基）Br（8），Ni（t tmiy）2（Me）I（9）和Ni（tmiy）2 I 2（10）。配合物8和10的X射线晶体结构据报道，其揭示了与卡宾配体