[(((2,6-i-Pr2C6H3)NC(t-Bu))2CH)Cr(μ-Cl)]2 | 1093076-14-2

• 英文名称: [(((2,6-i-Pr2C6H3)NC(t-Bu))2CH)Cr(μ-Cl)]2
• CAS: 1093076-14-2
• 化学式: C₇₀H₁₀₆Cl₂Cr₂N₄
• 分子量: 1178.54
• InChiKey: VGAUYFZLIBXFMV-HVTGMRBBSA-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-i-Pr2C6H3)NC(t-Bu))2CH)Cr(μ-Cl)]2 、 (2,2-二甲基丙基)锂 以 乙醚 为溶剂， 以51%的产率得到[((2,6-i-Pr2C6H3)NC(t-Bu))2CH)Cr(CH2t-Bu)]
  参考文献：
  名称：

  Understanding and Predicting Distorted T- versus Y-Geometries for Neutral Chromous Complexes Supported by a Sterically Encumbering β-Diketiminate Ligand

  摘要：

  A series of three-coordinate Cr(II) complexes sharing the common molecular fragment "(nacnac)Cr" (nacnac = [ArNC(Bu-t)](2)CH, Ar = 2,6-(Pr2C6H3)-Pr-i) were prepared via salt metathesis with the dimer [(nacnac)Cr(mu-Cl)](2). Single-crystal X-ray diffraction studies revealed that the complexes (nacnac)Cr(L) (L = (CH2BU)-B-t, CH3, CH2CH3, SiH{2,4,6-Me3C6H2}(2), O{2,6-(Pr2C6H3)-Pr-i}, N{CH3}(2)) represent a rare class of mononuclear, neutral chromium complexes with a three-coordinate high-spin chromous metal center. Depending on the nature of the third ligand, L-, these complexes can adopt either distorted T-shaped or Y-shaped coordination geometries, Density functional theory calculations and molecular orbital analyses in combination with a detailed molecular fragment energy decomposition were used to establish an intuitive concept of the key electronic structure patterns that determine the coordination geometry of preference. The frontier orbitals of the (nacnac)Cr(II) fragment direct pi-donating ligands to adopt Y-shaped geometry, whereas ligands that are primarily sigma-donors prefer T-shaped coordination. The relationship between electronics at the metal center and coordination geometry was extended to include the putative neutral three-coordinate high-spin complexes of Sc(II) and Mn(II), which are predicted to both adopt Y-shaped geometry.

  DOI：

  10.1021/ja803798b
• 作为产物：
  描述：

  chromium dichloride 、 Li[((C6H3(CH(CH3)2)2-2,6)NC(t-Bu)CHC(t-Bu)N(C6H3(CH(CH3)2)2-2,6)] 以 四氢呋喃 为溶剂， 以53.4%的产率得到[(((2,6-i-Pr2C6H3)NC(t-Bu))2CH)Cr(μ-Cl)]2
  参考文献：
  名称：

  Understanding and Predicting Distorted T- versus Y-Geometries for Neutral Chromous Complexes Supported by a Sterically Encumbering β-Diketiminate Ligand

  摘要：

  A series of three-coordinate Cr(II) complexes sharing the common molecular fragment "(nacnac)Cr" (nacnac = [ArNC(Bu-t)](2)CH, Ar = 2,6-(Pr2C6H3)-Pr-i) were prepared via salt metathesis with the dimer [(nacnac)Cr(mu-Cl)](2). Single-crystal X-ray diffraction studies revealed that the complexes (nacnac)Cr(L) (L = (CH2BU)-B-t, CH3, CH2CH3, SiH{2,4,6-Me3C6H2}(2), O{2,6-(Pr2C6H3)-Pr-i}, N{CH3}(2)) represent a rare class of mononuclear, neutral chromium complexes with a three-coordinate high-spin chromous metal center. Depending on the nature of the third ligand, L-, these complexes can adopt either distorted T-shaped or Y-shaped coordination geometries, Density functional theory calculations and molecular orbital analyses in combination with a detailed molecular fragment energy decomposition were used to establish an intuitive concept of the key electronic structure patterns that determine the coordination geometry of preference. The frontier orbitals of the (nacnac)Cr(II) fragment direct pi-donating ligands to adopt Y-shaped geometry, whereas ligands that are primarily sigma-donors prefer T-shaped coordination. The relationship between electronics at the metal center and coordination geometry was extended to include the putative neutral three-coordinate high-spin complexes of Sc(II) and Mn(II), which are predicted to both adopt Y-shaped geometry.

  DOI：

  10.1021/ja803798b