[N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamidato-κ2N,N](η3-benzyl)nickel | 869954-98-3

• 英文名称: [N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamidato-κ2N,N](η3-benzyl)nickel
• 英文别名: [N-(2,6-diisopropylphenyl)-2-(2,6-diisoprpylphenylimino)propanamidato-κ2N,N](η3-CH2Ph)nickel
• CAS: 869954-98-3
• 化学式: C₃₄H₄₄N₂NiO
• 分子量: 555.426
• InChiKey: HVOPMXFQOFONDQ-VVEZBVGFSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 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：

  吡啶 、 [N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamidato-κ2N,N](η3-benzyl)nickel 以 甲苯 为溶剂， 以95%的产率得到[N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamidato-κ2N,N](η1-benzyl)nickel(pyridine)
  参考文献：
  名称：

  单组分α-氨基甲酰胺镍乙烯聚合和共聚引发剂

  摘要：

  Ni（COD）2，苄基氯，N-（2,6-二异丙基苯基亚胺基）-2-（2,6-二异丙基苯基亚氨基）丙酰胺酸钾与吡啶或2,6-二甲基吡啶的反应生成N，O-结合的α-亚氨基羧酰胺配合物，可用作乙烯的均聚或乙烯与功能化降冰片烯单体共聚的单组分引发剂。Py和2,6-lutidine配合物的比较突出了氮配体的不稳定性如何影响聚合活性。另外，也可以合成η 1 -CH 2 COPH络合物通过这些过程，它们是稳定的，以较少官能单体的存在下进行。

  DOI：

  10.1021/om070155g
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 potassium N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamidate 、 氯化苄 在 2,3-二甲基苯胺 作用下， 以 四氢呋喃 为溶剂， 以70%的产率得到[N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamidato-κ2N,N](η3-benzyl)nickel
  参考文献：
  名称：

  α-Iminocarboxamide Nickel Complexes:  Synthesis and Uses in Ethylene Polymerization

  摘要：

  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.

  DOI：

  10.1021/om050640g