[(2,4-pentane-N,N′-bis(2,6-diisopropylphenyl)ketiminate)Cr(μ-I)]2 | 945907-78-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(2,4-pentane-N,N′-bis(2,6-diisopropylphenyl)ketiminate)Cr(μ-I)]2
• 英文别名: [chromium(II)(μ-iodide)(2,4-pentane N,N'-bis(2,6-diisopropylphenyl)diketiminate)]2；bis((bis(2,6-diisopropylphenyl)-2,4-ketiminato)(μ-iodo)chromium(V))；[Cr(μ-I)(CH(C(Me)NC6H3(iPr)2)2]2；[(i-Pr2Ph)2nacnacCr(μ-I)]2；[NniPrCr(μ-I)]2
• CAS: 945907-78-8
• 化学式: C₅₈H₈₂Cr₂I₂N₄
• 分子量: 1193.12
• InChiKey: MESFDSRQYVEKHF-IHVPEPGGSA-L

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：

  [(2,4-pentane-N,N′-bis(2,6-diisopropylphenyl)ketiminate)Cr(μ-I)]2 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 生成 [Cr(μ-NPh)(HC(C(Me)NC6H3-i-Pr2)2)]2
  参考文献：
  名称：

  Binding and Activation of Small Molecules by Three-Coordinate Cr(I)

  摘要：

  [(i-Pr2Ph)(2)nacnacCr](2)(mu-eta(2):eta(2)-N-2) (2) has been prepared and structurally characterized; it contains a bridging side-on bonded dinitrogen ligand with a N-N distance of 1.249(5) A. Reactions of this reactive Cr(I) synthon with various small molecules resulted in a series of unusual molecules and transformations; thus CO yielded the binuclear isocarbonyl [(i-Pr2Ph)(2)nacnacCr](2)(CO)(mu-eta(1):eta(1)-CO)(2), ethylene gave [(i-Pr2Ph)(2)nacnacCr](2)(mu-eta(2):eta(2)-C2H4), O-2 oxidatively added to produce (i-Pr2Ph)(2)nacnacCr(O)(2), and azobenzene afforded the product of NN bond cleavage [(i-Pr2Ph)(2)nacnacCr](2)(mu-NPh)(2). 2 can be prepared in good yield and affords a facile entry to low-coordinate Cr(I) coordination chemistry.

  DOI：

  10.1021/ja0725549
• 作为产物：
  描述：

  chromium(II) iodide 、 (2-((2,6-diisopropylphenyl)amino)-4-((2,6-diisopropylphenyl)imino)-pent-2-ene) lithium salt 以87%的产率得到[(2,4-pentane-N,N′-bis(2,6-diisopropylphenyl)ketiminate)Cr(μ-I)]2
  参考文献：
  名称：

  Binding and Activation of Small Molecules by Three-Coordinate Cr(I)

  摘要：

  [(i-Pr2Ph)(2)nacnacCr](2)(mu-eta(2):eta(2)-N-2) (2) has been prepared and structurally characterized; it contains a bridging side-on bonded dinitrogen ligand with a N-N distance of 1.249(5) A. Reactions of this reactive Cr(I) synthon with various small molecules resulted in a series of unusual molecules and transformations; thus CO yielded the binuclear isocarbonyl [(i-Pr2Ph)(2)nacnacCr](2)(CO)(mu-eta(1):eta(1)-CO)(2), ethylene gave [(i-Pr2Ph)(2)nacnacCr](2)(mu-eta(2):eta(2)-C2H4), O-2 oxidatively added to produce (i-Pr2Ph)(2)nacnacCr(O)(2), and azobenzene afforded the product of NN bond cleavage [(i-Pr2Ph)(2)nacnacCr](2)(mu-NPh)(2). 2 can be prepared in good yield and affords a facile entry to low-coordinate Cr(I) coordination chemistry.

  DOI：

  10.1021/ja0725549

文献信息

• A well-defined model system for the chromium-catalyzed selective oligomerization of ethylene
  作者：Wesley H. Monillas、John F. Young、Glenn P. A. Yap、Klaus H. Theopold

  DOI：10.1039/c3dt00109a

  日期：——

  The chromium(I) dinitrogen complex [(i-Pr2Ph)2nacnacCr]2(μ–η2:η2-N2) catalyzes the selective trimerization of ethylene to 1-hexene at ambient pressure and temperature, and in the absence of any cocatalyst. After the conversion of the substrate, the catalyst cleanly converts to another chromium(I) species, namely [(i-Pr2Ph)2nacnacCr]2(μ–η2:η2-C2H4), which is not catalytically active. Binuclear metallacycles containing Cr(II) have been prepared as candidates for catalytically active intermediates; however they are not kinetically competent to explain the catalysis. Turning thus to mononuclear metallacycles featuring Cr(III), a chromacyclopentane, chromacyclopentene and chromacyclopentadiene have been prepared as models of catalytic intermediates. Of these, the latter also catalyzes the trimerization of ethylene. These results support the proposal that selective ethylene oligomerization catalysis involves an interplay between Cr(I) ethylene complexes and mononuclear Cr(III) metallacycles.

  铬（I）二氮络合物[(i-Pr2Ph)2nacnacCr]2(μ-η2:η2-N2)在环境压力和温度下，在没有任何助催化剂的情况下，催化乙烯向 1-己烯的选择性三聚反应。底物转化后，催化剂会完全转化为另一种铬（I），即[(i-Pr2Ph)2nacnacCr]2(μ-η2:η2-C2H4)，后者没有催化活性。含有 Cr(II) 的双核金属环已被制备成具有催化活性的候选中间体，但它们在动力学上无法解释催化作用。因此，我们转向以 Cr(III) 为特征的单核金属环，制备了铬环戊烷、铬环戊烯和铬环戊二烯作为催化中间体模型。其中，后者还能催化乙烯的三聚反应。这些结果支持这样的观点，即选择性乙烯低聚催化涉及铬（I）乙烯络合物和单核铬（III）金属环之间的相互作用。
• The synthesis, characterization, and alkylation of nacnac chromium triflate derivatives
  作者：John F. Young、Leonard A. MacAdams、Glenn P.A. Yap、Klaus H. Theopold

  DOI：10.1016/j.ica.2010.08.010

  日期：2010.12

  A Cr(III) triflate coordinated by the bulky beta-diketiminate L-Me(iPr) (L-Me(iPr) = 2,4-pentane N,N'-bis(2,6-diisopropylphenyl)diketiminate) was synthesized from the corresponding bridging iodide complex [(LCr)-L-Me-Cr-iPr(mu-I)](2) by ligand substitution and subsequent oxidation with silver triflate (AgOTf). L-Me(iPr) Cr-III(OTf)(2) exhibits rare trigonal bipyramidal geometry about Cr(III). Attempts to alkylate this triflate synthon with 1,4-dilithiobutane (Li(CH2)(4)Li) led to reduction, while reaction with dimethylzinc (ZnMe2) led to a mono-alkylated product; only the reaction with methyl lithium (MeLi) was successful in generating a dialkyl. (C) 2010 Elsevier B.V. All rights reserved.
• Reactivity of a low-valent chromium dinitrogen complex
  作者：Wesley H. Monillas、Glenn P.A. Yap、Klaus H. Theopold

  DOI：10.1016/j.ica.2010.11.024

  日期：2011.4

  (Nn(iPr)Cr)2(mu(2)-kappa(2):kappa(2)-N-2) (1, Nn(iPr) = bis(2,6-diisopropylphenyl)pentane-2,4-ketiminato), formally a chromium(I) complex, was exposed to a variety of small molecules possessing hetero-or homo-atomic single, double, or triple bonds. Reaction of 1 with adamantyl azide yielded complexes in various higher oxidation states, such as (Nn(iPr)Cr(II))(2)(mu(2)-NAd) (2), Nn(iPr)Cr(III)(kappa(2)-N(4)Ad(2)) (3), or Nn(iPr)Cr(V)(NAd)(2) (4). Compound 1 was found to reductively couple 3-pentanone to form Nn(iPr)Cr(kappa(2)-O2C2Et4) (5) and reductively couple benzylidene aniline to form both Nn(iPr)Cr(III)(cis-kappa(2)-C28H22N2) (6a) an Nn(iPr)Cr(III)(trans-kappa(2)-C28H22N2) (6b). Reaction with a stochiometric amount of benzylidene aniline yielded the imine complex Nn(iPr)Cr(eta(2)-NPhCHPh) (7). Exposure of 1 to a bulky isocyanide formed the octahedral Nn(iPr)Cr(I)[CN(C6H4(Me)(2)](4) (9). Complex 1 was also found to break the O-O, N=O, and S-S bonds in various small molecules to form Nn(iPr)Cr(II)(OCMe3) (11), Nn(iPr)Cr(V)(O)(NPh) (8), and [Nn(iPr)Cr(II)(mu-SPh)](2) (10). (C) 2010 Elsevier B.V. All rights reserved.