[La(N,N′-bis(2,6-diisopropylphenyl)formamidinate-κ²N,N')₂(tetrahydrofuran)Me] | 1416400-80-0

• 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: [La(N,N′-bis(2,6-diisopropylphenyl)formamidinate-κ²N,N')₂(tetrahydrofuran)Me]
• 英文别名: [La(N,N′-bis(2,6-diisopropylphenyl)formamidinate)₂(thf)Me]；carbanide;[2,6-di(propan-2-yl)phenyl]-[[2,6-di(propan-2-yl)phenyl]iminomethyl]azanide;lanthanum(3+);oxolane
• CAS: 1416400-80-0
• 化学式: C₅₅H₈₁LaN₄O
• 分子量: 953.18
• InChiKey: OPBJJNCBNDDZNQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.34
• 重原子数：
  61
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  36
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [La(N,N′-bis(2,6-diisopropylphenyl)formamidinate-κ²N,N')₂(tetrahydrofuran)Me] 在 1,2,3,4-tetraphenylcyclopentadiene 作用下， 以 氘代苯 为溶剂， 生成 [La(N,N′-bis(2,6-diisopropylphenyl)formamidinate-κ²N,N')₃]
  参考文献：
  名称：

  Bulky Formamidinate-Supported Lanthanoid Halides and Alkyls, Including a Rare Terminal La–Me Species

  摘要：

  The oxidation of [Sm(DippForm)(2)(thf)(2)] (1; DippFormH = N,N'-bis(2,6-diisopropylphenyl)forrnamidine) by tert-butyl chloride, 1,2-dibromoethane, and iodine, respectively, at ambient temperature led to the isolation of the light yellow crystalline samarium(III) halide complexes [Sm(DippForm)(2)X(thf)] (2, X = Cl; 3, X = Br; 4, X = I) in good yield. The subsequent metathesis reaction of [Ln(DippForm)(2)X(thf)] (2, Ln = Sm, X = Cl; Ln = La, X = F) with LiMe and LiCH2SiMe3 generated the samarium alkyl complexes [Sm(DippForm)(2)R(thf)] (5, R = Me; 6, R = CH2SiMe3) and the rare terminal La-Me complex [La-(DippForm)(2)Me(thf)] (7). The attempted ligand exchange reaction of 7 with 1,2,3,4-tetraphenylcyclopentadiene gave, unexpectedly, the homoleptic tris-(formamidinato)lanthanum complex [La(DippForm)(3)] (8) in very low yield. The redox transmetalation/protolysis (RTP) reaction from samarium metal with bis(2-bromo-3,4,5,6-tetrafluorophenyl)mercury and DippFormH in thf yielded the mono(formamidinato)samarium(III) complex [Sm(DippForm)Br-2(thf)(3)] (9) as a coproduct with the bis(formamidinate) 3. Redox reaction of the divalent samarium complex [Sm(DippForm)(2)(thf)(2)] (1) with ciiphenylmercury resulted in the ethenolate complex [Sm(DippForm)(2)(OCH=CH2)(thf)] (10) instead of the target Sm-Ph complex, the product resulting from the decomposition of Lewis base thf molecules.

  DOI：

  10.1021/om301048b
• 作为产物：
  描述：

  [La(N,N′-bis(2,6-diisopropylphenyl)formamidinate)₂(tetrahydrofuran)F] 、 甲基锂 以 乙醚 、 甲苯 为溶剂， 反应 0.5h， 以48%的产率得到[La(N,N′-bis(2,6-diisopropylphenyl)formamidinate-κ²N,N')₂(tetrahydrofuran)Me]
  参考文献：
  名称：

  Bulky Formamidinate-Supported Lanthanoid Halides and Alkyls, Including a Rare Terminal La–Me Species

  摘要：

  The oxidation of [Sm(DippForm)(2)(thf)(2)] (1; DippFormH = N,N'-bis(2,6-diisopropylphenyl)forrnamidine) by tert-butyl chloride, 1,2-dibromoethane, and iodine, respectively, at ambient temperature led to the isolation of the light yellow crystalline samarium(III) halide complexes [Sm(DippForm)(2)X(thf)] (2, X = Cl; 3, X = Br; 4, X = I) in good yield. The subsequent metathesis reaction of [Ln(DippForm)(2)X(thf)] (2, Ln = Sm, X = Cl; Ln = La, X = F) with LiMe and LiCH2SiMe3 generated the samarium alkyl complexes [Sm(DippForm)(2)R(thf)] (5, R = Me; 6, R = CH2SiMe3) and the rare terminal La-Me complex [La-(DippForm)(2)Me(thf)] (7). The attempted ligand exchange reaction of 7 with 1,2,3,4-tetraphenylcyclopentadiene gave, unexpectedly, the homoleptic tris-(formamidinato)lanthanum complex [La(DippForm)(3)] (8) in very low yield. The redox transmetalation/protolysis (RTP) reaction from samarium metal with bis(2-bromo-3,4,5,6-tetrafluorophenyl)mercury and DippFormH in thf yielded the mono(formamidinato)samarium(III) complex [Sm(DippForm)Br-2(thf)(3)] (9) as a coproduct with the bis(formamidinate) 3. Redox reaction of the divalent samarium complex [Sm(DippForm)(2)(thf)(2)] (1) with ciiphenylmercury resulted in the ethenolate complex [Sm(DippForm)(2)(OCH=CH2)(thf)] (10) instead of the target Sm-Ph complex, the product resulting from the decomposition of Lewis base thf molecules.

  DOI：

  10.1021/om301048b