Ni(COD)(PMe3)2 | 101077-61-6

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: Ni(COD)(PMe3)2
• 英文别名: (1Z,5Z)-cycloocta-1,5-diene;nickel;trimethylphosphane
• CAS: 101077-61-6
• 化学式: C₁₄H₃₀NiP₂
• 分子量: 319.03
• InChiKey: OXSYOALOYBSPNB-PHFPKPIQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.39
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Ni(COD)(PMe3)2 、 双环[4.1.0]-1,3,5-庚三烯 以 正戊烷 为溶剂， 以87%的产率得到bismethano-nickelacyclotridecahexaene
  参考文献：
  名称：

  Mynott,Richard; Neidlein, Richard; Schwager, Harald, Angewandte Chemie, 1986, vol. 98, # 4, p. 374 - 376

  摘要：

  DOI：
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 三甲基膦 以 氘代苯 为溶剂， 生成 tetrakis(trimethylphosphine)nickel(0) 、 Ni(COD)(PMe3)2
  参考文献：
  名称：

  N-杂环卡宾-锆配合物中1,2-烷基向卡宾的可逆迁移和氨活化

  摘要：

  将三甲基膦添加到双（酚盐）苄基咪唑亚基（二苄基）锆络合物会诱导苄基配体从金属中心迁移到 C（卡宾）原子。这个过程可以逆转，导致 Csp(3)-Csp(3) 活化，通过提取膦，这是受管制的、可逆的烷基迁移的一个例子。向二苄基复合物中加入氨会导致一个苄基迁移和另一个苄基质子分解，从而通过 NMR 可观察的中间体 NH3 加合物生成双 (NH2) 桥接二聚体。

  DOI：

  10.1021/jacs.5b06695
• 作为试剂：
  描述：

  联苯烯 在 Ni(COD)(PMe3)2 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以92%的产率得到tetraphenylene
  参考文献：
  名称：

  串联钯，钴和镍催化的含环丁二烯，苯和环辛酸酯环的多环π系统的合成

  摘要：

  描述了一个序列，其中Co I在与炔烃共环化1,2-二乙炔基芳烃（相应的卤代芳烃的Pd II催化的炔基化反应）时提供催化剂，以提供取代的联苯，Ni 0用于将后者二聚为相应的四苯并环辛酸酯。该策略为合成和理论上感兴趣的新型多环π系统提供了一种新颖的合成途径。

  DOI：

  10.1016/0022-328x(90)85227-p

文献信息

• Metallaborane chemistry. Part V. Reactions of zerovalent nickel and platinum complexes with arachno-5,9-C2B7 carbaboranes; crystal and molecular structure of a carbadibora-allyl nickel complex
  作者：Michael Green、Judith A. K. Howard、John L. Spencer、F. Gordon A. Stone

  DOI：10.1039/dt9750002274

  日期：——

  and [Pt(C2B7H9Me2)(PPh3)2]. The parent arachno-5,9-C2B7H13 carbaborane also reacts with [Pt(PEt3)2(stilbene)] to give [Pt(C2B7H11)(PEt3)2]. A single crystal X-ray diffraction study on the nickel compound [6,6-(Et3P)2-5.9-Me2-6,5,9-NiC2B7H9] establishes that the metal atom is joined to a B2C-system in a 1,2,3-η bonding mode. This crystallizes in the monoclinic space group P21/n with Z= 4 in a unit

  环八-1,5-二烯双（三乙膦）镍与5,9-Me 2 -5,9-C 2 B 7 H 11的反应导致氢的逸出并形成[Ni（C 2 B 7 H 9 Me 2）（PEt 3）2 ]。C 2 B 7 H 11 Me 2与[Ni（PMe 3）2（cod）]，[Pt（PEt 3）2（二苯乙烯）]，[Pt（PMe 3）2（二苯乙烯）]或[铂（PPh 3）2（sti）]分别给出[Ni（C 2 B 7 H 9 Me 2）（PMe 3）2 ]，[Pt（C 2 B 7 H 9 Me 2）（PEt 3）2 ]，[Pt（C 2 B 7 H 11 Me 2）（PMe 3）2 ]和[Pt（C 2 B 7 H 9 Me 2）（PPh 3）2 ]。母arachno -5,9-C 2 B7 H 13碳硼烷也与[Pt（PEt 3） 2（二苯乙烯）]反应生成[Pt（C 2 B 7 H 11）（PEt 3） 2 ]。对镍化合物[6,6-（Et
• Methylnickel compounds containing 2-phosphinylethanolato ligands – Syntheses, properties, and ethene coupling reactions
  作者：Hans-Friedrich Klein、Mengzhen He、Olaf Hetche、Alexander Rau、Dirk Walther、Thomas Wieczorek、Gerhard Luft

  DOI：10.1016/j.ica.2005.07.030

  日期：2005.11

  methyl(methoxo)(trimethylphosphine)nickel gave mononuclear methyl(trimethylphosphine)nickel(chelate) compounds 7–9. Ligand 6 (R1 = Me, R2 = 4-OMe–C6H5) afforded a dinuclear methylnickel compound 14. By reacting (TMEDA)lithium-dimethylphosphinylmethanide with ketones O C(R1R2), the dimethylphosphinylethanols HO(R1R2)CCH2PMe2 (3: R1R2 = 9-fluorenyl; 4: R1 = H, R2 = C6H5) were synthesized as prechelate ligands. Under

  摘要将二甲基次膦基乙醇HO（R1R2）CCH2PMe2（1：R1 = R2 = C6H5; 2：R1 = R2 = 4-OMe–C6H4; 5：R1 = R2 = 4-NMe2- ）与甲基（甲氧基）（三甲基膦）镍结合得到单核甲基（三甲基膦）镍（螯合物）化合物7-9。配体6（R1 = Me，R2 = 4-OMe– ）得到双核甲基镍化合物14。通过使（TMEDA）锂-二甲基膦基甲甲烷与酮OC（R1R2）反应，二甲基膦基乙醇HO（R1R2）CCH2PMe2（3：R1R2 = 9 -芴基； 4：R 1 ＝ H，R 2 ＝ C 6 H 5）被合成为前螯合物。在其他相似的条件下，3中的芴基取代的阴离子会生成单核络合物10，发现该化合物可作为形成三核膦的双核11的来源，同时也可作为形成五配位的10·PMe3的三甲基膦的受体。Ni（COD）（PMe3）2在将8或9分别转化为双核甲基镍化合物12
• Nickel-mediated synthesis of dialkynyl and trialkynyl ethenes — demetallation reactions
  作者：Hans-Freidrich Klein、Andreas Peterman

  DOI：10.1016/s0020-1693(97)05485-6

  日期：1997.9

  Metalorganic syntheses of the title compounds starting from l-alkynes and Ni(cod)(PMe3)(2) or Ni(PM3)(4) consist of less than six steps and afford better than 50% overall yields of isolated compounds. Elimination of the metal by reductive C,C coupling in diorganonickel complexes under 1 bar CO and workup in aqueous hydrochloric acid are the key steps in the preparation af(RC=C)R'C=C(R) (C=CR) (R=SiMe3, CMe3; R'=H, CH3, C6H5, C=CH, C=CCH3, C=CCMe3, C=CSiMe3, C=CSiPh3, C=CC6H5, C=CC6H4F, C=CC6H11, C=CCH2SiMe3). Starting from 3-bromopropyne the initial C,C-coupling reaction is followed by an oxidative addition of the CH,Br function to zerovalent nickel and a second C,C coupling, which generates the tetradecadienetetrayne skeleton of (RC=C)(R)C=(RC=C)C-C=C-CH2-CH2-C=C-(RC=C)C=C(C=CR)-(R) (R=SiMe3).
• Organometallic Nickelamacrocycles of the Type [(R₂R‘P)Ni(C₂H₄COO)]<i>_n</i>:  Synthesis and Self-Assembly to Form Different Molecular Architectures Tuned by the Phosphine
  作者：Jens Langer、Helmar Görls、Reinald Fischer、Dirk Walther

  DOI：10.1021/om040111x

  日期：2005.1.1

  The reaction of succinic anhydride with a 1:2 mixture of (cod)(2)Ni and a monodentate phosphine generates reactive monomeric nickelalactones, which undergo rapid aggregation to form cyclic oligomers of the composition [(R2R'P)Ni(C2H4COO)](n) (R2R'P = EtPh2P (2), Me3P (4), (i-Pr)(3)P (5), Cy3P (6), Et3P (7)). The complexes were fully characterized by elemental analyses (except 4), NMR and IR spectroscopy, and X-ray crystallography of single crystals. Depending on the bulkiness of the phosphines, three types of nickelamacrocycles with different ring size and different connectivity pattern of the monomeric units are formed. The small Me3P stabilizes a cyclic tetramer (n = 4) in which the units are linked by Ni-O-Ni bonds. This bridge is stable in thf solution. The bulkiest phosphines stabilize another type of cyclotetrameric architecture in 2, 5, and 6, in which the monomeric units are connected by Ni-O-C=O bridges. In contrast, 7, stabilized by the Et3P ligand, forms a hexacyclic compound (n = 6) with Ni-O-C=O bridges. The IR spectrum of 7 in thf shows two C=O valence frequencies, indicating that at least two species are present in which the carboxylate group is differently coordinated (Ni-O and Ni-O-C=O-Ni coordination).
• Syntheses and properties of molecular nickel(II) hydride, methyl, and nickel(I) complexes supported by trimethylphosphane and (2-diphenylphosphanyl)thiophenolato and -naphtholato ligands
  作者：Peter B. Kraikivskii、Markus Frey、Hamdi A. Bennour、Armin Gembus、Ralf Hauptmann、Ingrid Svoboda、Hartmut Fuess、Vitaly V. Saraev、Hans-Friedrich Klein

  DOI：10.1016/j.jorganchem.2009.01.023

  日期：2009.5

  2-Diphenylphosphanyl) thiophenol (PpSH) or (3-diphenylphosphanyl)-2-thionaphthol (PnSH) react with Ni(PMe3)(4) to form NiH(PpS)(PMe3)(2) (1) or NiH(PnS)(PMe3)(2) (2). 1,3-Bis(diphenylphosphanyl) propane (PP) replaces the monodentate phosphane ligands to give NiH(PpS)(PP) (3). NiMe(OMe)(PMe3) or NiMe2(PMe3)(3) react with PpSH to form NiMe(PpS)(PM3) (4) and NiMe( PpS)( PMe3)(2) (5), respectively, and PnSH affords NiMe(PnS)(PMe3)(2) (6), NiMe(PnS)(PMe3) (7). Dissociation of PMe3 ligands induces transformation of 1 to Ni(PpS)(PMe3)(2) (8) and Ni(PpS)(2). Crystal and molecular structures are given for 1, 5- 8, and dynamic solution spectra (NMR, EPR) are discussed. (C) 2009 Elsevier B.V. All rights reserved.