[PrCl₃(1,2-dimethoxyethane)] | 266353-00-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [PrCl₃(1,2-dimethoxyethane)]
• 英文别名: [PrCl3(dme)]；1,2-dimethoxyethane;trichloropraseodymium
• CAS: 266353-00-8
• 化学式: C₄H₁₀Cl₃O₂Pr
• 分子量: 337.389
• InChiKey: ZSJZSWNVPGBRJL-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  [PrCl₃(1,2-dimethoxyethane)] 、 二氧化碳 、 二异丙胺 以 甲苯 为溶剂， 生成 [Pr(N,N-diisopropylcarbamato)3]4
  参考文献：
  名称：

  N,N-二烷基氨基甲酸镧络合物，一系列同型配位化合物

  摘要：

  [Ln(O2CNR2)3] (Ln = Pr, Nd, Eu, Gd, Ho, Er, Yb, Lu, R = iPr; Ln = Nd, Eu, Gd ，R = Bu；Ln = Nd，R = Et)，使用 [LnCl3(ether)x]（醚 = THF 或二甲氧基乙烷，DME），报告了 NHR2 和 CO2。二异丙基氨基甲酸衍生物的 X 射线衍射，包括对 [Yb4(O2CNiPr2)12] 的重新研究，表明这些配合物在 12 个原子序数的范围内是四核和同型的。基于四种不同类型的 Ln-O 键的长度评估了镧系元素收缩。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejic.200300649

文献信息

• Tetrahydropentalenyl-phosphazene constrained geometry complexes of rare-earth metal alkyls
  作者：Noa K. Hangaly、Alexander R. Petrov、Michael Elfferding、Klaus Harms、Jörg Sundermeyer

  DOI：10.1039/c3dt53596g

  日期：——

  [Lu(CH2SiMe3)3(thf)2] or with rare-earth metal halides and three equivalents of LiCH2SiMe3 produced the desired bis(alkyl) Cp™PN complexes: [Cp™PN}M(CH2SiMe3)2] (M = Sc (1Ad, 1Dip), Lu (2Ad, 2Dip), Y (3Ad, 3Dip), Sm (4Ad), Nd (5Ad), Pr (6Ad), Yb (7Ad)). These complexes were characterized by extensive NMR studies for the diamagnetic and the paramagnetic complexes with full signal assignment. An almost

  Cp™HPPh 2（1，二苯基（4,4,6,6-四甲基-1,4,5,6-四氢戊二烯-2-基）膦）与有机叠氮化物AdN 3和DiPN 3（Ad = 1 -金刚烷基； Dip = 2,6-二异丙基苯基）导致形成两个新的CpPN配体：P-氨基-环戊二烯叉叉基-正膦（Cp™PPh 2 NHAd；L Ad H）和P-环戊二烯基-亚氨基正膦（ Cp™HPPh 2 NDip; L浸入H）。两者均通过NMR光谱和X射线结构分析来表征。对于这两种化合物，仅观察到一种异构体。两者都不具有任何可检测到的质子或元亲异构体。这些配体与[Lu（CH 2 SiMe 3）3（thf）2 ]或与稀土金属卤化物和三当量的LiCH 2 SiMe 3的反应产生了所需的双（烷基）Cp™PN络合物：[Cp™ PN} M（CH 2 SiMe 3）2 ]（M = Sc（1 Ad，1 Dip），Lu（2 Ad，2 Dip），Y（3Ad，3
• Cyclopentadienylphosphazene (CpPN) Complexes of Rare-Earth Metals: Synthesis, Structural Characterization, and Hydroamination Catalysis
  作者：Noa K. Hangaly、Alex R. Petrov、Konstantin A. Rufanov、Klaus Harms、Michael Elfferding、Jörg Sundermeyer

  DOI：10.1021/om200264n

  日期：2011.9.12

  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.