(Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)YbCl(tetrahydrofuran)2 | 856422-46-3

• 英文名称: (Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)YbCl(tetrahydrofuran)2
• 英文别名: (Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)YbCl(THF)2；[YbCl(Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)(THF)2]；[((Me3SiNC(C6H5)N)2C3H6)YbCl(THF)2]
• CAS: 856422-46-3
• 化学式: C₃₁H₅₀ClN₄O₂Si₂Yb
• 分子量: 775.428
• InChiKey: OQVJNAZJURSJEF-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：

  (Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)YbCl(tetrahydrofuran)2 在 Na/K 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以60%的产率得到[Yb3(μ2-Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)3]
  参考文献：
  名称：

  桥联双（酰胺基）L [L = Me 3 SiN（Ph）CN（CH 2）3 NC（Ph）NSiMe 3 ]支撑的二价镧系元素配合物：合成，分子结构和单电子转移反应

  摘要：

  YbI 2与Li 2 L（L = Me 3 SiN（Ph）CN（CH 2）3 NC（Ph）NSiMe 3）在THF中的复分解反应，摩尔比为1：1和1：2均得到Yb（··································································································································································································则II）碘化物络合物[{YbI（DME）2 } 2（μ 2 -L）]（1），其在结构上表征为双核镱（II）配合物与桥接大号配体。EUI的治疗2与Li 2大号未得到类似的[{EUI（DME）2 } 2（μ 2 -L）]，或其他可分离的铕（II）络合物，但是六核的异簇[{李（DME）3

  DOI：

  10.1021/ic202505d
• 作为产物：
  描述：

  四氢呋喃 、 (Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)Yb(μ-Cl)2Yb(Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)(tetrahydrofuran) 以 正己烷 为溶剂， 以57%的产率得到(Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3)YbCl(tetrahydrofuran)2
  参考文献：
  名称：

  连接的双（脒）镱配合物的合成、反应性和结构表征

  摘要：

  摘要 连接的双（脒）双阴离子配体 LLi2 [L=Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3] 的二锂盐与无水 YbCl3 在 THF 中以 1:1 的摩尔比反应，从己烷中结晶后，得到连接的双（脒）氯化镱LYb（μ-Cl）2YbL（THF）（1）。配合物 1 中的氯桥很容易被供体溶剂破坏。在 THF 存在下从己烷中重结晶配合物 1 形成单体氯化镱 LYbCl(THF)2 (2)。络合物 2 与 1 当量的反应。后处理后，CpNa 以高产率得到所需的镱复合物 LYbCp(DME) (3)。所有配合物均通过元素分析、红外光谱和单晶X射线衍射表征。

  DOI：

  10.1016/j.molstruc.2005.02.027

文献信息

• Bridged bis(amidinate) lanthanide aryloxides: syntheses, structures, and catalytic activity for addition of amines to carbodiimides
  作者：Jing Tu、Wenbo Li、Mingqiang Xue、Yong Zhang、Qi Shen

  DOI：10.1039/c3dt33069a

  日期：——

  Various lanthanide aryloxide complexes supported by bridged bis(amidinate) ligand L, LLnOAr(DME) (L = Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3, DME = dimethoxyethane, 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)) were synthesized, and complexes 1, 2 and 4–6 were characterized by single crystal X-ray diffraction. All the complexes are efficient precatalysts for catalytic addition of amines to carbodiimides. The catalytic activity is influenced by lanthanide metals and the aryloxide groups (Nd (4) ∼ Sm (5) < Y (3) ∼ Yb (6) and -2,6-(Me)2C6H3 < -2,6-(iPr)2C6H3 < -2,6-(tBu)2-4-(Me)C6H2). The catalytic addition reaction with 3 showed a good scope of substrates. The mechanism investigation revealed the real active intermediate being the monoguanidinate complexes supported by an aryloxide and an amidine-functionalized amidinate group, L′Ln[O2,6-(tBu)2-4-(Me)C6H2][RNCNHRN(Ar′)] (L′ = Me3SiNHC(Ph)N(CH2)3NC(Ph)NSiMe3, R = iPr, Ar′ = phenyl, Ln = Yb (8), Y (11); R = Cy, Ar′ = phenyl, Ln = Yb (10), Y (12); R = iPr, Ar′ = 4-ClC6H4, Ln = Yb (9)), which were isolated from the reactions of 6 (or 3) with amine and carbodiimide in a molar ratio of 1 : 1 : 1 and structurally characterized. The Ln-active group in the present precatalyst is a Ln–amidinate species, not the Ln–OAr group.

  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) ，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) ）。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) ][RNCNHRN(Ar′)]（L′ = Me3SiNHC(Ph)N( )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。
• 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）
• Ytterbium amides of linked bis(amidinate): synthesis, molecular structures, and reactivity for the polymerization of l-lactide
  作者：Junfeng Wang、Tao Cai、Yingming Yao、Yong Zhang、Qi Shen

  DOI：10.1039/b709310a

  日期：——

  bis(amidinate) is coordinated to the metal center as a chelating ligand. The similar reaction with NaN(SiMe3)2 afforded a bimetallic amide complex (TMS)2NYb(L)2YbN(TMS)23 formed through the rearrangement reaction of L induced by the bulky N(SiMe3)2 group. In complex 3 the two linked bis(amidinate)s act as bridging ancillary ligands to link two YbN(TMS)2 species in one molecule. The definite molecular structures

  酰胺基对连接双（ami基）L（L = [Me 3 SiNC（Ph）N（CH 2）3 NC（Ph）NSiMe 3 ]）负载的酰胺的合成，分子结构和反应性的空间影响被报道。LYbCl（THF）2与等摩尔的NaNHAr'和NaNHAr（Ar'= 2,6-Me 2 C 6 H 3； Ar = 2,6- i Pr 2 C 6 H 3）分别反应，得到相应的单金属酰胺配合物LYb（NHAr'）（DME）1和LYb（NHAr）（DME）2，其中连接的双（ami基）作为螯合物与金属中心配位配体。与NaN（SiMe 3）2的相似反应得到双金属酰胺配合物（TMS）2 NYb（L）2 YbN（TMS）2 3是由庞大的N（SiMe 3）2基团引起的L的重排反应形成的。在复合物3中，两个链接的双（酰胺基）起到桥接辅助分子的作用配体在一个分子中连接两个YbN（TMS）2物种。单晶提供了1-3的确定分子结构X射线分析。配
• 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
• Bridged bis(amidinate) lanthanide complexes: Synthesis, molecular structure and reactivity
  作者：Junfeng Wang、Hongmei Sun、Yingming Yao、Yong Zhang、Qi Shen

  DOI：10.1016/j.poly.2008.03.006

  日期：2008.6

  The yttrium chloride with the bridged bis(amidinate) L (L = Me3SiNC(Ph)N(CH2)(3)NC(Ph)NSiMe3) LYCl(DME) (2) was synthesized and structurally characterized. Treatment of LLnCl(sol)(x) (Ln = Yb, sol = THF, x = 2 1; Ln = Y, sol = DME, x = 1 2) with the dilithium salt Li2L(THF)(0.5) afforded the novel bimetallic lanthanide complexes supported by three ligands, Ln(2)(mu(2)-L)(3)center dot DME (Ln = Yb 3, Y 4; DME = dimethylether), instead of the designed complex LLn(mu(2)-L)LnL via the ligand redistribution reaction. Complexes 3 and 4 were fully characterized including X-ray analysis and H-1 NMR spectrum for 4. Reaction of LnCl(3) (Ln = Yb, Y) with 2 equiv. of Li2L(THF)(0.5) gave the anionic complexes [Li(DME)(3)] [L(2)Ln] (Ln = Yb 5, Y 6), which were confirmed by a crystal structure determination. The further study indicated that complexes 3 and 4 can also be synthesized by reaction of LnCl(3) (Ln = Yb, Y) with 1.5 equiv. of Li2L(THF)0.5 or reaction of 1 and 2 with anionic complexes 5 and 6. Complexes 3, 4, 5 and 6 were found to be high active catalysts for ring-opening polymerization of c-caprolactone (CL). (C) 2008 Elsevier Ltd. All rights reserved.