(η1-CH2Ph)NiCl(PMe3)2 | 120058-69-7

• 英文名称: (η1-CH2Ph)NiCl(PMe3)2
• 英文别名: (η¹-CH2Ph)NiCl(PMe3)2；[Ni(η1-benzyl)Cl(trimethylphosphine)2]；[Ni(PMe3)2(η1-benzyl)Cl]；[Ni(η1-CH2Ph)Cl(PMe3)2]；[Ni(PMe3)2(η1-CH2Ph)Cl]；[NiCl(η1-CH2Ph)(PMe3)2]；NiCl(η1-benzyl)(PMe3)2
• CAS: 120058-69-7
• 化学式: C₁₃H₂₅ClNiP₂
• 分子量: 337.432
• InChiKey: GBGYOZSJCZDFPA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (η1-CH2Ph)NiCl(PMe3)2 以 四氢呋喃 为溶剂， 生成 [Ni(η3-benzyl)(C(CCH3O)(CCH3OB(C6F5)3)C(CH3)N(C6H3(CH(CH3)2)2))]
  参考文献：
  名称：

  用于乙烯低聚的镍催化剂的远程活化。

  摘要：

  DOI：

  10.1002/anie.200461630

文献信息

• Vinyl polymerizations of norbornene catalyzed by nickel complexes with acetoacetamide ligands
  作者：Qian Feng、Dajun Chen、Danyang Feng、Libin Jiao、Zhigang Peng、Lixia Pei

  DOI：10.1002/aoc.3067

  日期：2014.1

  Norbornene polymerizations with acetoacetamide nickel complexes activated with modified methylaluminoxane (MMAO) were investigated in detail. Remote steric and electronic effects of acetoacetamide ligand on catalytic activity and molecular weight of polynorbornenes (PNBs) were observed. Characterizations of the obtained PNBs show that the obtained polymer products are non‐crystalline vinylic‐addition

  基于远程效应，一系列乙酰乙酰胺配体和相应的镍络合物N-（R-苯基）乙酰乙酰胺Ni（CH 2 Ph）（PMe 3）（R  =  H，1 ; R  =  2-甲基，2 ; [R  =  2,6-二甲基，3 ; R  =  2,6-二异丙基，4 ; R  =  4-NO 2，5）的合成和表征。X射线单晶分析证实了配合物3的固体结构为顺式。1 H和311 H NMR光谱证实溶液中存在镍配合物的顺式和反式异构体。详细研究了用改性甲基铝氧烷（MMAO）活化的乙酰乙酰胺镍配合物的降冰片烯聚合反应。观察到乙酰乙酰胺配体对聚降冰片烯（PNBs）的催化活性和分子量的远程空间和电子效应。所获得的PNB的表征表明，所获得的聚合物产物是非晶态的乙烯基加成聚降冰片烯。版权所有©2013 John Wiley＆Sons，Ltd.
• Nickel Catalysts Activated by rGO Modified with a Boron Lewis Acid To Produce rGO-Hyperbranched PE Nanocomposites
  作者：Sebastián A. Correa、Constantin G. Daniliuc、H. Sophia Stark、René S. Rojas

  DOI：10.1021/acs.organomet.9b00397

  日期：2019.9.9

  The synthesis, characterization, and ethylene reactivity of a nickel-activated α-cyano-β-ketoiminate complex with B(C6F5)3 is reported. The X-ray diffraction studies of the Ni complex 1 revealed that a weak interaction between the distal aryl rings of the N-terphenyl moiety could be responsible for the low molecular weights and highly branched microstructure of the polyethylene compounds. In addition

  报道了镍活化的α-氰基-β-酮亚胺酸盐与B（C 6 F 5）3的合成，表征和乙烯反应性。Ni配合物1的X射线衍射研究表明，N-三联苯基部分的远端芳环之间的弱相互作用可能是聚乙烯化合物的低分子量和高度支化的微观结构的原因。此外，使用了基于还原性氧化石墨烯的负载型单中心路易斯酸，rGO-OB（C 6 F 5）2，我们研究了其活化复合物1的能力。用于产生聚乙烯/还原的氧化石墨烯纳米复合材料。负载型催化剂rGO-B（C 6 F 5）2 -Ni CN表现出的乙烯聚合活性约为未负载体系的乙烯聚合活性的两倍。同时，通过13 C NMR对聚乙烯纳米复合材料的微观结构进行了分析，结果表明，由于存在sec，因此存在低分子量和超支化的基序。丁基。这些结果表明，石墨烯载体积极地参与了聚合过程。通过TEM对纳米复合材料的形态学检查表明，rGO在纳米级水平上有效剥落并良好地分散在聚合物基质中。
• Bulky and Electron‐Deficient α‐Iminocarboxamidato‐Nickel(II) Complexes: A Study of the Steric and Electronic Effects on Ethylene Activation
  作者：Leon Skarjan、Nery Villegas‐Escobar、Sebastián A. Correa、Constantin G. Daniliuc、Ricardo A. Matute、René S. Rojas

  DOI：10.1002/ejic.202100474

  日期：2021.10.26

  and revealed that adduct formation is thermodynamically favored for small Lewis acids such as BF 3 due to the sterically demanding ligand environment of the complex, confirming the experimental findings. DFT results associate the lack of polymerization activity with a highly unfavorable steric environment, undesirable London dispersion interactions between the ligands, and a strong electrostatic stabilization

  合成了两种含有配体和几个 CF 3 基团的α-亚氨基甲酰胺基镍 (II) 配合物，并通过核磁共振光谱、元素分析和密度泛函理论 (DFT) 计算表征。令人惊讶的是，所制备的复合物在尝试使用常见路易斯酸助催化剂如 B(C 6 F 5 ) 3 和 BF 3 进行活化时对乙烯低聚物/聚合反应无活性。使用量子化学计算并表明，由于配合物的空间要求严格的配体环境，加合物形成在热力学上对小路易斯酸如 BF 3 有利，这证实了实验结果。DFT 结果将缺乏聚合活性与非常不利的空间环境、配体之间不希望的伦敦分散相互作用、以及由所采用的配体引起的强静电稳定性。我们的发现应该有助于未来的研究人员确定这些化合物所需的电子和空间要求，以生成活性 Ni(II) 催化剂，用于由合适的硼路易斯酸活化的乙烯低聚/聚合。
• Binding modes of a dimethyliminopentanone ligand on nickel pre-catalysts toward olefin polymerization
  作者：Brycelyn M. Boardman、Guang Wu、Rene Rojas、Guillermo C. Bazan

  DOI：10.1016/j.jorganchem.2008.12.038

  日期：2009.4

  Nickel complexes prepared using a 4-(2,6-diisopropylphenylimino)-3,3-dimethylpentan-2-one ligand framework are shown. The potassium salt of the ligand is obtained by deprotonation with KH in diethyl ether. Potassium 4-(2,6-diisopropylphenylimino)-3,3-dimethyl-pent-2-en-2-olate can then be reacted with Ni(PMe3)2(η1-CH2Ph)Cl to yield 4-(2,6-diisopropylphenylimino)-3,3-dimethyl-pent-2-en-2-olato-κ1O](η1-CH2Ph)(PMe3)2Ni

  显示了使用4-（2,6-二异丙基苯基亚氨基）-3,3-二甲基戊烷-2-一配体骨架制备的镍配合物。配体的钾盐是通过在乙醚中用KH脱质子化而获得的。钾4-（2,6-二异丙基苯基亚氨基）-3,3-二甲基-戊-2-烯-2-醇盐然后可以与反应的Ni（PME 3）2（η 1 -CH 2 PH）氯，得到4- （2,6-二异丙基苯基亚氨基）-3,3-二甲基-戊-2-烯-2- olato-κ 1 ö ]（η 1 -CH 2 PH）（PME 3）2的Ni（1）。的配体的钾盐，也可以用Ni（PME反应3）（η 3 -CH 2PH）氯，得到双（4-（2,6-二异丙基苯基亚氨基）-3,3-二甲基-戊-2-烯-2- olato-κ 2 N，O ]（η 1个-CH 2 PH）2的Ni 2（2）或4-（2,6-二异丙基苯基亚氨基）-3,3-二甲基-戊-2-烯-2- olato-κ 2 N，O ]（η 1 -CH 2 PH）（PME
• α-Iminocarboxamide Nickel Complexes:  Synthesis and Uses in Ethylene Polymerization
  作者：Rene S. Rojas、Julia-Christina Wasilke、Guang Wu、Joseph W. Ziller、Guillermo C. Bazan

  DOI：10.1021/om050640g

  日期：2005.11.1

  A series of nickel complexes containing alpha-iminocarboxamide, eta(1)-benzyl, and PMe(3) ligands were synthesized to identify structural features of neutral Ni complexes that are employed in ethylene polymerization and ethylene/functionalized norbornene copolymerizations. Variations in steric bulk on aryl substituents in the alpha-iminocarboxamide framework were used to probe NN-versus N,O-binding modes. When the steric bulk is sufficiently large, as in [N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamidato-kappa(2)N,O]Ni(eta(1)-CH(2)Ph)(PMe3) (1), [N-(2,6-diethylphenyl)-2-(2,6-diethylphenylimino)propanamidato-kappa(2)N,O](eta(1)-CH(2)Ph)(PMe(3))nickel (2), and [N-(2,6-methyl-isopropylphenyl)-2-(2,6-methylisopropylphenylimino)propanamidato-kappa(2)N,O](eta(1)-CH(2)Ph)(PMe3)nickel (3), one observes NO-binding. In the case of [N-(2,6-dimethylphenyl)-2-(2,6-dimethylphenylimino)propanamidatol ((eta(1)-CH(2)Ph)(PMe(3))nickel (4), both, N,O- and N,N-bound modes can be obtained and isolated; the N,N structure is the thermodynamic product. N,N products are observed with smaller ligands, as in [N-phenyl-2-(2,6-diisopropylphenylimino)propanamidato-kappa(2)N,N](eta(1)-CH(2)Ph)(PMe(3))nickel (5) and [N-(2,6-diisopropylphenyl)-2-(phenylimino)propanamidato-kappa(2)N,N](eta(1)-CH(2)Ph)(PMe(3))nickel (6). Ethylene polymerization, upon activation with Ni(COD)(2), is observed only with the NO-bound species. NMR spectroscopy shows that addition of Ni(COD)2 to 5 and 6 results in removal of the phosphine and the formation of an eta(3)-benzyl fragment. Furthermore, the phosphine-free complex [N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamidato-kappa(2)N,N](eta(3)-CH(2)Ph)nickel (7) is also inactive toward ethylene polymerization. These observations suggest that ethylene polymerization is preferentially initiated by nickel complexes with NO-bound alpha-iminocarboxamide ligands.