La2(μ-NH-2,6-i-Pr2C6H3)2(NH-2,6-i-Pr2C6H3)4 | 713141-05-0

• 英文名称: La2(μ-NH-2,6-i-Pr2C6H3)2(NH-2,6-i-Pr2C6H3)4
• 英文别名: [La(μ-NHC6H3iPr-2,6)(NHC6H3(i-Pr)2-2,6)2]2
• CAS: 713141-05-0
• 化学式: C₇₂H₁₀₈La₂N₆
• 分子量: 1335.5
• InChiKey: TWYLUNJKRXOUBO-UHFFFAOYSA-N

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：

  La2(μ-NH-2,6-i-Pr2C6H3)2(NH-2,6-i-Pr2C6H3)4 、 三甲基铝 以 正己烷 、 甲苯 为溶剂， 以0%的产率得到[(μ-NC6H3(i-Pr)2-2,6)La(μ-NHC6H3iPr-2,6)(μ-Me)AlMe2]2
  参考文献：
  名称：

  The First Example of a μ₂-Imido Functionality Bound to a Lanthanide Metal Center:  X-ray Crystal Structure and DFT Study of [(μ-ArN)Sm(μ-NHAr)(μ-Me)AlMe₂]₂ (Ar = 2,6-ⁱPr₂C₆H₃)¹

  摘要：

  Reaction of 3 equiv of 2,6-diisopropylaniline with Sm[N(SiMe3)(2)](3) affords the dimeric species [Sm(NHAr)(3)](2) (1). X-ray crystallography illustrates that each metal center in 1 engages in an eta(6)-arene interaction with the aryl ring of an amide ligand attached to an adjacent samarium. IR spectroscopy indicates that the pi-arene interactions are maintained in solution. Reaction of 1 with 4 equiv of trimethylaluminum leads to formation of the bis(mu(2)-imido) complex [(mu-ArN)Sm(mu-NHAr)(mu-Me)AlMe2](2) (2). The molecular structure of 2 contains a unique central Sm2N2 core which displays extremely short bridging Sm-N distances of 2.152(8) and 2.271(7) Angstrom, characteristic of an imido complex. Density functional theory (DFT) calculations have been carried out in order to gain a better understanding of the nature of the bonding interactions within complex 2 and indicate that the 5d metal acceptor orbitals play a significant role in stabilizing pi-donation from the imido groups to the samarium centers within the Sm2N2 core.

  DOI：

  10.1021/om0206960
• 作为产物：
  描述：

  La(NH-2,6-i-Pr2C6H3)3(THF)3 以 甲苯 为溶剂， 生成 La2(μ-NH-2,6-i-Pr2C6H3)2(NH-2,6-i-Pr2C6H3)4
  参考文献：
  名称：

  A Comparative Study of π-Arene-Bridged Lanthanum Arylamide and Aryloxide Dimers. Solution Behavior, Exchange Mechanisms, and X-ray Crystal Structures of La₂(NH-2,6-ⁱPr₂C₆H₃)_6, La(NH-2,6-ⁱPr₂C₆H₃)₃(THF)₃, and La(NH-2,6-ⁱPr₂C₆H₃)₃(py)₂

  摘要：

  Reaction of 3 equiv of 2,6-diisopropylaniline with La[N(SiMe3)(2)](3) produces the dimeric species La-2(NHAr)(6) (1). X-ray crystallography reveals a centrosymmetric structure, where the dimeric unit is bridged by intermolecular eta(6)-arene interactions of a unique arylamide ligand attached to an adjacent metal center. Exposure of 1 to THF results in formation of the monomeric tris-THF adduct La(NHAr)3(THF)3 (2), which was shown by X-ray crystallography to maintain a fac-octahedral structure in the solid state. H-1 NMR spectroscopy illustrates that the binding of THF to 1 to form 2 is reversible and removal of THF under vacuum regenerates dimeric 1. Addition of pyridine to 1 yields the monomeric bis-pyridine adduct La(NHAr)(3)(py)(2) (3), which exhibits a distorted trigonal-bipyramidal La metal center. Solution H-1 NMR, IR, and Raman spectroscopy indicate that the pi-arene-bridged dimeric structure of 1 is maintained in solution. Variable-temperature H-1 NMR spectroscopic investigations of 1 are consistent with a monomer-dimer equilibrium at elevated temperature. In contrast, variable-temperature H-1 NMR spectroscopic investigations of the aryloxide analogue La-2(OAr)(6) (4) show that the bridging and terminal aryloxide groups exchange by a mechanism in which the dimeric nature of the compound is retained. Density functional theory (DFT) calculations were carried out on model compounds La-2(OC6H5)(6), La-2(NHC6H5)(6), and (C6H5R)La(XC6H5)(3), where X = O or NH and R = H, OH, or NH2. The formation of eta(6)-arene interactions is energetically favored over monomeric LaX3 (X = OPh or NHPh) with the aryloxide pi-arene interaction being stronger than the arylamide T-arene interaction. Calculation of vibrational frequencies reveals the origin of the observed IR spectral behavior of both La-2(OC6H5)(6) and La-2(NHC6H5)(6), with the higher energy nu(C=C) stretch due to terminal ligands and the lower energy stretch associated with the bridging ligands.

  DOI：

  10.1021/ja0398262