[((2,6-diisopropylphenyl)N=CH-CH=N(2,6-diisopropylphenyl))Cr(μ-Cl)]2 | 960322-22-9

• 英文名称: [((2,6-diisopropylphenyl)N=CH-CH=N(2,6-diisopropylphenyl))Cr(μ-Cl)]2
• 英文别名: [(N,N'-bis(2,6-diisopropylphenyl)-1,4-diazadiene)Cr(μ-Cl)]2；[((2,6-diisopropylphenyl)N=CH)2CrCl]2
• CAS: 960322-22-9
• 化学式: C₅₂H₇₂Cl₂Cr₂N₄
• 分子量: 928.068
• InChiKey: DPMMYMZMUXFDTN-LKLZSUSMSA-L

计算性质

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

反应信息

• 作为反应物：
  描述：

  [((2,6-diisopropylphenyl)N=CH-CH=N(2,6-diisopropylphenyl))Cr(μ-Cl)]2 在 KC₈ 作用下， 以 乙醚 为溶剂， 生成 (μ-η2-N,N'-bis(2,6-diisopropylphenyl)-1,4-diazadiene(2-))2Cr2
  参考文献：
  名称：

  迄今为止最短的金属-金属键：双核铬二氮杂二烯配合物的分子和电子结构

  摘要：

  用 KC8 还原二氮杂二烯卤化铬络合物 [(HLiPr)Cr(μ-Cl)]2 (1, HLiPr = 双(2,6-二异丙基苯基)二氮杂二烯)，得到抗磁性双金属络合物 (HLiPr)2Cr2 ( 2）。配合物 2 已通过 X 射线晶体学在结构上表征，由两个二氮杂二烯配体跨越的 Cr2 单元组成。非常短的 Cr−Cr 距离 (1.8028(9) A) 和 Cr 原子的低形式氧化态表明 Cr−Cr 键序可能大于 4。模型复合体上的自旋受限和自旋非受限 DFT 计算两者都收敛于单重自旋状态并准确再现了 2 的度量参数。计算显示高阶金属 - 金属键合以及二氮二烯配体上的广泛离域。自然共振理论分析显示包含五重键的共振结构群，

  DOI：

  10.1021/ja076356t
• 作为产物：
  描述：

  trichlorotris(tetrahydrofuran)chromium(III) 、 以 四氢呋喃 为溶剂， 生成 [((2,6-diisopropylphenyl)N=CH-CH=N(2,6-diisopropylphenyl))Cr(μ-Cl)]2
  参考文献：
  名称：

  Synthesis, Characterization, and Electronic Structure of Diimine Complexes of Chromium

  摘要：

  We have prepared and structurally characterized several complexes of chromium coordinated by diimine (or 1,4-diazadiene) ligands, that is, Ar-N = C(R)-(R)C = N - Ar (L-R(Ar)) (where Ar = 2,6-diisopropylphenyl ('' iPr '') or 2,6-dimethylphenyl ('' Me '') and R = H or Me). The reaction of CO2 with L-H(iPr) gave dinuclear [(L-H(iPr))Cr](2)(mu-Cl)(3)(Cl)(THF) when isolated from Et2O; in THF solution, however, the product exists as mononuclear (L-H(iPr))CrCl2(THF)(2). Two isostructural derivatives, (L-Me(Me))CrCl2(THF)(2) and (L-H(Me))CrCl2(THF)(2), have also been prepared. Furthermore, the bis-ligand complex, (L-H(iPr))(2)Cr, has been prepared along with its reduction product, Li(THF)(4)[(L-H(iPr))(2)Cr]. We have also synthesized the tetracarbonyl complex, (L-H(iPr))Cr(CO)(4), by addition of L-H(iPr) to Cr(CO)(4)(NCCH3)(2). The structure and variable temperature magnetic susceptibility of the previously reported Cr halide dimer, [(L-H(iPr))Cr(mu-Cl)](2), is also discussed in detail. All of the diimine complexes have been characterized structurally, spectroscopically, and magnetically, and their electronic structures are discussed with the aid of density-functional theory calculations.

  DOI：

  10.1021/ic800302w

文献信息

• Organochromium Complexes Bearing Noninnocent Diimine Ligands
  作者：Kevin A. Kreisel、Glenn P. A. Yap、Klaus H. Theopold

  DOI：10.1002/ejic.201100803

  日期：2012.1

  complexes featuring noninnocent α-diimine ligands. All neutral and anionic complexes refrain from insertion of the C=N bonds of the diimine ligand into the chromium–carbon bonds, presumably due to the reduced nature of the diimine ligand. However, insertion can be facilitated by one-electron oxidation. Thus, oxidation of [(HLiPr)CrR(THF)] [HLiPr = Ar–N=C(H)–(H)C=N–Ar in which Ar = 2,6-diisopropylphenyl

  我们已经制备了几种阴离子和中性有机铬配合物，其特征是非无辜的 α-二亚胺配体。所有中性和阴离子配合物都避免将二亚胺配体的 C=N 键插入铬-碳键，这可能是由于二亚胺配体的性质减少。然而，单电子氧化可以促进插入。因此，[(HLiPr)CrR(THF)] [HLiPr = Ar–N=C(H)–(H)C=N–Ar 其中 Ar = 2,6-二异丙基苯基和 R = CH2SiMe3 或 CH3] 的氧化[(C5H5)2Fe]+ 可能形成 [(HLiPr)CrR(THF)]+，其中包含与 CrII 配位的中性二亚胺配体。这种阳离子配合物显然会立即将二亚胺配体的 C=N 键插入 Cr-烷基键中，然后 C-H 活化二亚胺配体上 N-芳基的异丙基取代基。