[Nb(1,4-diisopropyl-1,4-diazabuta-1,3-diene)3] | 421551-49-7

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: [Nb(1,4-diisopropyl-1,4-diazabuta-1,3-diene)3]
• CAS: 421551-49-7
• 化学式: C₂₄H₄₈N₆Nb
• 分子量: 513.592
• InChiKey: OQDRRXJYAAFNME-SYCOSPNZSA-N

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：

  [Nb(1,4-diisopropyl-1,4-diazabuta-1,3-diene)3] 、 silver tetraphenylborate 以 not given 为溶剂， 生成 [Nb(1,4-diisopropyl-1,4-diazabuta-1,3-diene)3][BPh4]
  参考文献：
  名称：

  Stable Formally Zerovalent and Diamagnetic Monovalent Niobium and Tantalum Complexes Based on Diazadiene Ligands

  摘要：

  This paper describes the efficient synthesis and full characterization of rare formally zerovalent and diamagnetic monovalent pseudooctahedral niobium and tantalum complexes. The reaction of NbCl(4)(thf)(2) with 4 equiv of Na and 3.5 equiv of iPr(2)-dad (1,4-diisopropyl-1,4-diaza-1,3-diene) yields Nb(iPr(2)-dad)(3) in 52% yield. Ta(iPr(2)-dad)(3) is also obtained in 33% yield from 5 equiv of Na/naphthalene and 3.5 equiv of iPr(2)-dad. Oxidation of these complexes with AgBPh(4) yields the diamagnetic complexes [M(iPr(2)-dad)(3)][BPh(4)] (M = Nb, Ta). X-ray and spectroscopic data indicate that the unpaired electron density is localized on the ligands. DFT calculations reveal that, in the prevailing D(3) symmetry, a very strong splitting of t(2g) metal-based orbitals occurs, leading to the diamagnetism of the 16e M(iPr(2)-dad)(3)(+). This strong splitting allows a M-N nonbonding, ligand-based orbital to accommodate additional electrons, as a result of which the formally zerovalent complexes, M(iPr(2)-dad)(3), are in fact correctly formulated as M(+)iPr(2)-dad (-), that is, (16e + 1e).

  DOI：

  10.1021/ja017303t
• 作为产物：
  描述：

  四氯双(四氢呋喃)合铌(IV) 、 N,N'-二异丙基乙烷-1,2-二亚胺 在 Na 作用下， 以 乙二醇二甲醚 、 N,N-二甲基甲酰胺 为溶剂， 以52%的产率得到[Nb(1,4-diisopropyl-1,4-diazabuta-1,3-diene)3]
  参考文献：
  名称：

  Stable Formally Zerovalent and Diamagnetic Monovalent Niobium and Tantalum Complexes Based on Diazadiene Ligands

  摘要：

  This paper describes the efficient synthesis and full characterization of rare formally zerovalent and diamagnetic monovalent pseudooctahedral niobium and tantalum complexes. The reaction of NbCl(4)(thf)(2) with 4 equiv of Na and 3.5 equiv of iPr(2)-dad (1,4-diisopropyl-1,4-diaza-1,3-diene) yields Nb(iPr(2)-dad)(3) in 52% yield. Ta(iPr(2)-dad)(3) is also obtained in 33% yield from 5 equiv of Na/naphthalene and 3.5 equiv of iPr(2)-dad. Oxidation of these complexes with AgBPh(4) yields the diamagnetic complexes [M(iPr(2)-dad)(3)][BPh(4)] (M = Nb, Ta). X-ray and spectroscopic data indicate that the unpaired electron density is localized on the ligands. DFT calculations reveal that, in the prevailing D(3) symmetry, a very strong splitting of t(2g) metal-based orbitals occurs, leading to the diamagnetism of the 16e M(iPr(2)-dad)(3)(+). This strong splitting allows a M-N nonbonding, ligand-based orbital to accommodate additional electrons, as a result of which the formally zerovalent complexes, M(iPr(2)-dad)(3), are in fact correctly formulated as M(+)iPr(2)-dad (-), that is, (16e + 1e).

  DOI：

  10.1021/ja017303t