[CeCl3(dme)] | 662109-75-3

• 英文名称: [CeCl3(dme)]
• CAS: 662109-75-3
• 化学式: C₄H₁₀CeCl₃O₂
• 分子量: 336.601
• InChiKey: CRFQHAZPDYDFDS-UHFFFAOYSA-K

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：

  P-(1-adamantylamino)-P-dimethyl-tetramethyl-cyclopentadienylidene-phosphorane 、 [CeCl3(dme)] 、 trimethylsilylmethyllithium 以 乙醚 、 甲苯 为溶剂， 以53%的产率得到[(η5,η1-C5Me4PMe2NAd)Ce(CH2SiMe3)2]
  参考文献：
  名称：

  Cyclopentadienylphosphazene (CpPN) Complexes of Rare-Earth Metals: Synthesis, Structural Characterization, and Hydroamination Catalysis

  摘要：

  Synthesis of the first series of rare-earth-metal constrained geometry complexes containing the P-(1-adamantylamino)-P-dimethyl-tetramethyl-cyclopentadienylidene-phosphorane ligand C(5)Me(4)PMe(2)NHAd, {(CpPN)-P-#}H, was accomplished. This monoanionic chelate ligand is isoelectronically related to the classical dianionic cyclopentadienyl-silylamine ligand C5Me4HSiMe2-NHtBu, {(CpSiN)-Si-#}H-2. The ligand stabilizes dialkyls [{(CpPN)-P-#}M(CH2SiMe3)(2)] (M = Sc, 1; Lib 2; Y, 3; Sm, 4; Nd, 5; Pr, 6; Ce, 7) over the full range of group 3 and lanthanide cation radii. Results of NMR studies of these crystalline alkyls, XRD molecular structures, and a preliminary study revealing the high catalytic activity of complexes 3-6 in the intramolecular hydroamination/cyclization are reported. The catalytic experiments reveal a trend in activity Lu < Y < Sm < Nd <= Pr resembling the trend in rare-earth-metal radii. Interestingly they reveal a distinctive substrate-dependent first-order kinetic profile for all metals investigated. The reaction of the precatalyst 3 with 1.6 equiv of the standard substrate 2,2-dimethylpenten-4-ylamine leads to a fast and selective formation of substrate complex [{(CpPN)-P-#}Y(NHCH2CMe2CH2CH-=CH2)(2)] (8). Fast cyclization was observed only after addition of more than 2 equiv of amine substrate. A noninsertive mechanism involving a six-membered transition state by a concerted C-N bond formation and N-H bond cleavage at a 3:1 substrate to complex ratio is suggested on the basis of these findings.

  DOI：

  10.1021/om200264n