((Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3))NdCl(THF)2 | 1383435-20-8

• 英文名称: ((Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3))NdCl(THF)2
• 英文别名: [((Me3SiNC(C6H5)N)2C3H6)NdCl(THF)2]
• CAS: 1383435-20-8
• 化学式: C₃₁H₅₀ClN₄NdO₂Si₂
• 分子量: 746.628
• InChiKey: XQCJGBXBXVMJHI-UHFFFAOYSA-M

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：

  乙二醇二甲醚 、 ((Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3))NdCl(THF)2 、 sodium 2,6-di-tert-butyl-4-methylphenoxide 以 四氢呋喃 为溶剂， 以78%的产率得到(Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)Nd[O2,6-(tBu)2-4-(Me)C6H2](DME)
  参考文献：
  名称：

  Bridged bis(amidinate) lanthanide aryloxides: syntheses, structures, and catalytic activity for addition of amines to carbodiimides

  摘要：

  合成了多种由桥接双氨基配体L支持的镧系元素芳氧化合物复合物LLnOAr(DME)（L = Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3，DME = 二甲氧基乙烷，Ln = Y，Ar = 2,6-(Me)2C6H3 (1)，2,6-(iPr)2C6H3 (2)，2,6-(tBu)2-4-(Me)C6H2 (3)；Ar = 2,6-(tBu)2-4-(Me)C6H2，Ln = Nd (4)，Sm (5)，Yb (6)），并通过单晶X射线衍射对复合物1、2和4–6进行了表征。所有复合物都是催化胺与氨基二烯烃加成反应的有效前催化剂。催化活性受镧系金属和芳氧基团的影响（Nd (4) ∼ Sm (5) < Y (3) ∼ Yb (6) 和 -2,6-(Me)2C6H3 < -2,6-(iPr)2C6H3 < -2,6-(tBu)2-4-(Me)C6H2）。与3的催化加成反应显示了良好的底物范围。机制研究揭示了实际活性中间体是由芳氧基和氨基功能化的氨基配体组支持的单氨基化合物复合物L′Ln[O2,6-(tBu)2-4-(Me)C6H2][RNCNHRN(Ar′)]（L′ = Me3SiNHC(Ph)N(CH2)3NC(Ph)NSiMe3，R = iPr，Ar′ = 苯基，Ln = Yb (8)，Y (11)；R = Cy，Ar′ = 苯基，Ln = Yb (10)，Y (12)；R = iPr，Ar′ = 4-ClC6H4，Ln = Yb (9)），这些复合物是通过6（或3）与胺和氨基二烯烃按1 : 1 : 1的摩尔比例反应而获得，并进行结构表征。本研究中的前催化剂中的Ln活性组分是Ln–氨基化物物种，而不是Ln–OAr基团。

  DOI：

  10.1039/c3dt33069a

文献信息

• Synthesis, characterization of bridged bis(amidinate) lanthanide amides and their application as catalysts for addition of amines to nitriles for monosubstituted N-arylamidines
  作者：Wenbo Li、Mingqiang Xue、Fan Xu、Jing Tu、Yong Zhang、Qi Shen

  DOI：10.1039/c2dt30400g

  日期：——

  showed a good scope of aromatic amines. Some key reaction intermediates were isolated and structurally characterized, including the amidinate complexes LLn[NPhCNAr1](PhCN) (Ln = Y (8), Ln = Yb (9)), LYb[NAr2CNAr1](Ar2CN) (10), and amide complex 5 prepared by protonation of 9 by Ar1NH2. Reactivity studies of these complexes suggest that the present catalytic formation of monosubstituted N-arylamidines

  桥联双（酰胺基）配体L，LLnNHAr 1（DME）（L = [Me 3 SiNC（Ph）N（CH 2）3 NC（Ph）NSiMe 3 ]，Ar 1 = 2， 6- i Pr 2 C 6 H 3，DME =二甲氧基乙烷，Ln为Y（1），PR（2），钕（3），钆（4），镱（5）），镱（μ 2 -NHPh）] 2（μ 2 -L）2（6）和[LYB] 2（μ 2 -NHAr 2）2（7）（AR 2 =（ø -OMe）C 6 H ^ 4），由LLnCl（THF）的反应，合成2用相应的酰胺酰胺以高收率得到产物，并通过X射线晶体结构分析对其结构进行表征。发现所有络合物都是用于将芳族胺催化加成到芳族腈中以得到单取代的N-芳基idine啶的预催化剂。镧系金属和酰胺基的催化活性受镧系金属和-NHAr 2 <的活性序列Y（1）
• Syntheses and structures of lanthanide borohydrides supported by a bridged bis(amidinate) ligand and their high activity for controlled polymerization of ε-caprolactone, l-lactide and rac-lactide
  作者：Wenbo Li、Mingqiang Xue、Jing Tu、Yong Zhang、Qi Shen

  DOI：10.1039/c2dt30096f

  日期：——

  Metathesis reaction of LLnCl(THF)2 [L = (Me3SiNC(C6H5)N)2(CH2)3] with NaBH4 in a 1 : 1.5 molar ratio in THF (THF = tetrahydrofuran) at 60 °C afforded the monoborohydride LLn(BH4)(DME) [Ln = Y (1), Nd (2), Sm(3) and Yb(4)] crystallized from DME solution (DME = dimethoxyethane). Crystal structure analyses revealed 1–4 are monomers, in which each metal is ligated by one L ligand, one η3-BH4 group and one DME molecule in a trigonal bipyramid geometry. Complexes 1–4 were found to be very active single-site initiators for the controlled ring opening polymerization of ε-caprolactone (ε-CL) and L-lactide (L-LA) as judged by relatively narrow molecular weight distributions (Mw/Mn: 1.34–1.50) and experimental values Mn(exp) were in good agreement with theoretic values Mn(theo). The highest activity and the best control over the molecular weight for both monomers were found for the system with 2. These monoborohydride complexes can also initiate the ring opening polymerization of rac-LA to gave heterotactically enriched polyLA with Pr (heterotactic enrichment) values in a range of 0.69–0.85 depending on the lanthanide metals and the most effective heterotactic enrichment (Pr) was found for 1 (Pr = 0.85). Moreover, complex 1 initiated the polymerization of rac-LA in a living fashion.

  LLnCl(THF)2 [L = (Me3SiNC(C6H5)N)2(CH2)3]与Na 在THF（THF =四氢呋喃）中以1∶1.5的摩尔比在60°C下发生复分解反应，生成从DME溶液（DME =二甲氧基乙烷）结晶的单硼氢化物LLn(BH4)(DME) [Ln = Y (1)、Nd (2)、Sm(3)和Yb(4)]。晶体结构分析显示1-4是单体，其中每个金属以三角双锥几何结构与一个L配体、一个Γ3- 基团和一个DME分子结合。根据相对较窄的分子量分布（Mw/Mn：1.34-1.50）和实验值Mn（exp）与理论值Mn（theo）的吻合程度，发现1-4是控制Μ-己内酯（Μ-CL）和L-丙交酯（L-LA）开环聚合的非常活跃的单点引发剂。在2的体系中，两种单体的活性最高，分子量控制效果最好。这些单硼氢化物复合物还可以引发rac-LA的开环聚合，生成异构富集的聚LA，根据镧系金属的不同