Cp*Ni(PMe3)(NHTol) | 174355-58-9

• 英文名称: Cp*Ni(PMe3)(NHTol)
• CAS: 174355-58-9
• 化学式: C₂₀H₃₂NNiP
• 分子量: 376.145
• InChiKey: BQJSZWOPYGULET-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：
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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：
  None

反应信息

• 作为产物：
  描述：

  [Cp*Ni(μ-NHTol)]2 、 三甲基膦 以 氘代苯 为溶剂， 生成 Cp*Ni(PMe3)(NHTol)
  参考文献：
  名称：

  Synthesis, Characterization, Isomerization, and Reactivity of Dimeric Cyclopentadienylnickel Amido Complexes

  摘要：

  The first cyclopentadienylnickel amido complexes have been isolated and characterized as [(eta-C(5)Me(4)R')Ni(mu-NHR)](2) (R = Ph, p-tol, 2,6-xyl, (t)Bu; R' = Me, Et). These complexes are dimers in solution and in the solid state, as shown by the synthesis of mixed amido complexes, by NMR spectroscopy, and by crystallographic studies on cis-[Cp(Et)Ni(mu-NH(p-tol))](2) (cis-1'), trans-[Cp(Et)Ni(mu-NH(2,6-xylyl))](2) (trans-3'), and cis-[Cp(Et)Ni(mu-NH(t)Bu)](2) (4') (Cp(Et) = eta-C(5)Me(4)Et). Resonances in the H-1 NMR spectra of these diamagnetic dimers display unusual chemical shifts that are explained on the basis of ring-current anisotropy and inductive effects. The dimers undergo reversible cis/trans isomerization at elevated temperatures; mechanistic studies indicate that this process proceeds through cleavage of one dative nitrogen-nickel bond, rate-limiting rotation of the amido group, and recoordination to regenerate the bridge. Dimethylzirconocene was essential as a scavenger for trace water in these studies. The dimer [Cp*Ni(mu-NH(p-tol))](2) (1) reacts with CO and with (t)BuNC to give the insertion products Cp*Ni(CO)(C(O)NH(p-tol)) (6) and Cp*Ni(CN(t)Bu)(C(N(t)Bu)NH(p-tol)) (7), respectively, and with PMe(3) to give the unstable monomeric amido complex Cp*Ni(PMe(3))(NH(p-tol)) (5).

  DOI：

  10.1021/ja952882l

文献信息

• Monomeric Cyclopentadienylnickel Methoxo and Amido Complexes:  Synthesis, Characterization, Reactivity, and Use for Exploring the Relationship between H−X and M−X Bond Energies
  作者：Patrick L. Holland、Richard A. Andersen、Robert G. Bergman、Jinkun Huang、Steven P. Nolan

  DOI：10.1021/ja971829p

  日期：1997.12.1

  nickel amide to be synthesized and the latter is the first structurally characterized monomeric nickel methoxide complex. The amido complex Cp*Ni(PEt3)NHTol reacts with various Bronsted acids (HX) to produce complexes of the type Cp*Ni(PEt3)X (X = NHAr, OR, Osilica, SR), and compounds with hydridic hydrogens to give the hydridonickel complex Cp*Ni(PEt3)H. The polarity of Ni−N and Ni−O bonds is also

  反应性单体酰氨基和甲氧配合物，Cp*Ni(PEt3)NHTol 和 Cp*Ni(PEt3)OMe，已被合成并充分表征。前者是第一个合成的单体 18 电子氨基镍，后者是第一个结构特征的单体甲醇镍配合物。酰胺络合物 Cp*Ni(PEt3)NHTol 与各种布朗斯台德酸 (HX) 反应生成 Cp*Ni(PEt3)X 类型的络合物（X = NHAr、OR、Osilica、SR），以及带有氢的化合物，生成氢化镍配合物 Cp*Ni(PEt3)H。Ni-N 和 Ni-O 键的极性也可以通过与碱金属盐和三甲基氯硅烷的反应以及 Cp*Ni(PEt3)OTol 的苯酚加合物的晶体学和 NMR 表征来证明。Cp*Ni(PEt3)X (X = OTol, SAr) 化合物通过缔合机制与 PMe3 交换；速率随着 X 的电负性而增加。 Cp*Ni(PEt3)X + HX' 和 Cp*Ni(PEt3)X' + HX'