lithium bis(trimethylsilyl)amide diethyl etherate | 18400-61-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: lithium bis(trimethylsilyl)amide diethyl etherate
• 英文别名: lithium hexamethyldisilazide diethyl etherate；[(Et₂O)Li(bis(trimethylsilyl)amide)]；bis(trimethylsilyl)amidolithium-diethyl ether；lithium bis(trimethylsilyl)amide-diethyl ether；lithiumbis(trimethylsilyl)amide-etherate；lithium hexamethyldisilazide diethyl ether；Li(N(SiMe3)2)*Et2O；(Me3Si)2NLi(Et2O)；Et2O*LiN(SiMe3)2；LiN(TMS)2*Et2O；Lithium;bis(trimethylsilyl)azanide;ethoxyethane；lithium;bis(trimethylsilyl)azanide;ethoxyethane
• CAS: 18400-61-8
• 化学式: C₄H₁₀O*C₆H₁₈LiNSi₂
• 分子量: 241.45
• InChiKey: OGRGWJKPBMGASO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.08
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  10.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  lithium bis(trimethylsilyl)amide diethyl etherate 在 potassium tert-butylate 作用下， 以 苯 为溶剂， 以79%的产率得到双(三甲基硅烷基)氨基钾
  参考文献：
  名称：

  β-氧代-δ-二亚胺镍络合物：乙烯聚合催化中互变异构活性物质的比较

  摘要：

  报道了一系列β-氧代-δ-二亚胺（BODDI）配体的单金属和双金属镍烷基配合物。单金属配合物具有第二个结合袋，其中的游离“臂”可以作为烯胺（例如，8，BODEI，β-氧代-δ-烯胺亚胺）或亚胺（例如，3，BODII，β-氧代- δ-亚胺亚氨基）互变异构体。二级 Ni 配位球中互变异构体的特性对乙烯聚合行为有显着影响：与中心 O 原子氢键并与 N、O 骨架螯合物共轭的烯胺互变异构体明显更富电子，并且产生比亚胺互变异构体低得多的分子量聚合物，亚胺互变异构体从Ni旋转到远端位置并且对聚合几乎没有影响。用 M(HMDS) 对第二个结合口袋进行去质子化 (M = Li, Na, K) 产生 Ni-碱金属异双金属配合物 3Li、3Na 和 3K。去质子化的碱金属烯酰胺表现出与中性亚胺复合物相似的乙烯聚合行为...

  DOI：

  10.1021/acs.organomet.6b00256
• 作为产物：
  描述：

  乙醚 、 六甲基二硅氮烷 在 正丁基锂 作用下， 以88%的产率得到lithium bis(trimethylsilyl)amide diethyl etherate
  参考文献：
  名称：

  β-氧代-δ-二亚胺镍络合物：乙烯聚合催化中互变异构活性物质的比较

  摘要：

  报道了一系列β-氧代-δ-二亚胺（BODDI）配体的单金属和双金属镍烷基配合物。单金属配合物具有第二个结合袋，其中的游离“臂”可以作为烯胺（例如，8，BODEI，β-氧代-δ-烯胺亚胺）或亚胺（例如，3，BODII，β-氧代- δ-亚胺亚氨基）互变异构体。二级 Ni 配位球中互变异构体的特性对乙烯聚合行为有显着影响：与中心 O 原子氢键并与 N、O 骨架螯合物共轭的烯胺互变异构体明显更富电子，并且产生比亚胺互变异构体低得多的分子量聚合物，亚胺互变异构体从Ni旋转到远端位置并且对聚合几乎没有影响。用 M(HMDS) 对第二个结合口袋进行去质子化 (M = Li, Na, K) 产生 Ni-碱金属异双金属配合物 3Li、3Na 和 3K。去质子化的碱金属烯酰胺表现出与中性亚胺复合物相似的乙烯聚合行为...

  DOI：

  10.1021/acs.organomet.6b00256
• 作为试剂：
  描述：

  对氯苯甲腈 在 lithium bis(trimethylsilyl)amide diethyl etherate 、 盐酸 、 sodium hydroxide 作用下， 以 乙醚 、 乙醇 、 水 为溶剂， 以53.7%的产率得到对氯苯甲脒
  参考文献：
  名称：

  Unsymmetrical 1λ³-1,2,4,6-Thiatriazinyls with Aryl and Trifluoromethyl Substituents: Synthesis, Crystal Structures, EPR Spectroscopy, and Voltammetry

  摘要：

  A general synthetic route to 3-trifluoromethyl-5-aryl-1 lambda(3)-1,2,4,6-thiatriazinyl radicals was developed. X-ray structures were obtained for all five neutral radicals and show that they exist in the solid state as cofacial dimers linked by S center dot center dot center dot S contacts. X-ray structures were also obtained for two of the precursor chlorothiatriazines along with several aryl N-imidoylamidines, p-methoxybenzamidine, and N-chlorosulfonyl-N,N'-benzamidine. Cyclic voltammetric studies were performed on the [R2C2N3S](center dot) radicals in CH3CN and CH2Cl2 with ["Bu4N][PF6] as the supporting electrolyte under vacuum conditions in an all-glass electrochemical cell. The results provide quasi-reversible formal potentials for the [R2C2N3S](-/0) process in the range of 0.61 to 0.47 V, irreversible peak potentials for the [R2C2N3S](0/+) process from 0.59 to 0.91 V at lower concentrations, and the appearance of a second, reversible oxidation process from 0.69 to 0.94 V at higher concentrations (versus the Fc(0/+). couple; Fc = ferrocene). This behavior was indicative of monomer dimer equilibrium in solution, as ascertained from digital models of the voltammograms. There is a small but measurable trend in both the oxidation and reduction potentials with varying remote aryl substituents. EPR spectra were obtained for all five neutral radicals in CH2Cl2 solutions, which confirm the concentration of the unpaired electron density on the heterocyclic core. Trends were also seen in the hyperfine splitting constants a(N) with varying remote aryl substituents. Calculations were performed for all three oxidation states of the [R2C2N3S](-/center dot/+) monomeric rings; the resulting theoretical redox energies correlate well with solution phase voltammetric data.

  DOI：

  10.1021/ic2003996

文献信息

• Subvalent Group 4B metal alkyls and amides. Part I. The synthesis and physical properties of kinetically stable bis[bis(trimethysilyl)methyl]-germanium(II), -tin(II), and -lead(II)
  作者：Peter J. Davidson、David H. Harris、Michael F. Lappert

  DOI：10.1039/dt9760002268

  日期：——

  described for the synthesis of the unusual bivalent Group 4B metal alkyls M[CH(SiMe3)2]2(M = Ge, Sn,or Pb)from Li[CH(SiMe3)2] indiethyl ether at 0 to –20°C and (a) the metal(II) chloride (M = Sn or Pb) or (b) M[N(SiMe3)2]2(M = Ge or Sn). At ambient temperature in cyclohexane or benzene the solutions are yellow (Ge), red (Sn), or purple (Pb), and the compounds are monomeric and in a singlet electronic ground

  两种方法用于不寻常的二价基团4B金属的合成烷基M [CH（森达描述3）2 ] 2选自Li（M =锗，锡，或Pb）[CH（森达3）2 ] indiethyl醚在0℃至–20°C和（a）氯化金属（II）（M = Sn或Pb）或（b）M [N（SiMe 3）2 ] 2（M = Ge或Sn）。在环境温度下，在环己烷或苯中，溶液为黄色（Ge），红色（Sn）或紫色（Pb），并且化合物为单体且呈单峰电子基态。固体和熔体之间会发生颜色变化，并且这些化合物在–196°C时趋于无色。锡的晶体结构（Ⅱ））烷基显示出一个中心对称的二聚体，其Sn-Sn键（2.76Å）的长度与Sn 2 Ph 6中的相似，并且两对双键烷基互为反式排列。由于在300 cm –1处存在强极化拉曼线，因此可以推断出该固体锗化合物在结构上相似。据信该单体在金属上与三个近似sp 2杂化的轨道成角，其中一个是非键合的；另一个是非键合的。二聚体。通
• Scandium and yttrium complexes of the diamide–diamine donor ligand (2-C5H4N)CH2N(CH2CH2NSiMe3)2: chloride, primary and secondary amide, benzamidinate and alkyl functionalised derivatives
  作者：Michael E. G. Skinner、Philip Mountford

  DOI：10.1039/b111469g

  日期：2002.4.9

  Five- and six-coordinate scandium and yttrium complexes of the recently described diamide–diamine donor ligand N2NN′ (where H2N2NN′ = (2-C5H4N)CH2NCH2CH2N(H)SiMe3}2) are described. Reaction of ScCl3 with Li2N2NN′ gave five-coordinate [ScCl(N2NN′)] 1 in excellent yield. The corresponding reaction with YCl3 in tetrahydrofuran (thf) or pyridine (py) solution afforded “ate” complexes best described as [YCl(N2NN′)(L)]·1.5(LiCl) (L = thf 2 or py 3). The two chloride complexes 1 and 2 are useful starting materials for primary and secondary amide, benzamidinate and alkyl complexes of Sc and Y supported by the N2NN′ ligand. Thus reaction of 1 or 2 with LiN(SiMe3)2·Et2O, LiNMe2 or LiNHR (R = tBu or Ar, where Ar = 2,6-C6H3iPr2) gave the corresponding five-coordinate amide derivatives [M(NRR″)(N2NN′)] (M = Sc, R = R″ = SiMe34 or Me 6, or R = H, R″ = tBu 8 or Ar 9; M = Y, R = R″ = SiMe35, or R = H, R″ = Ar 10). The crystal structure of 5 is described. The σ-bond metathesis reaction of [Sc(NMe2)(N2NN′)] 6 with ArFNH2 (ArF = C6F5) gave the corresponding primary flurophenylamide derivative 7. The reaction of 1 or 2 with Li[PhC(NSiMe3)2] gave the fluxional, six-coordinate benzamidinate derivatives [MPhC(NSiMe3)2}(N2NN′)] (M = Sc 11 or Y 12), the crystal structures of which are reported. Finally, reaction of 1 with LiCH2SiMe3 formed the alkyl derivative [Sc(CH2SiMe3)(N2NN′)] 13 in reasonable yield; the crystal structure of 13 is described.

  最近报道的二酰胺-二胺供体配体N2NN'（其中H2N2NN' = (2-C5H4N)CH2NCH2CH2N(H)SiMe3}2）的五配位和六配位钪和钇配合物。将ScCl3与Li2N2NN'反应得到了高产率的五配位[ScCl(N2NN')] 1。在四氢呋喃（thf）或吡啶（py）溶液中，将YCl3与Li2N2NN'反应得到了最佳描述为[YCl(N2NN')(L)]·1.5(LiCl)的“ate”配合物（L = thf 2或py 3）。两种氯配合物1和2是制备由N2NN'配体支撑的Sc和Y的一级和二级酰胺、苯甲酰亚胺和烷基配合物的重要起始材料。因此，将1或2与LiN(SiMe3)2·Et2O、LiNMe2或LiNHR（R = tBu或Ar，其中Ar = 2,6-C6H3iPr2）反应得到了相应的五配位酰胺衍生物[M(NRR')(N2NN')]（M = Sc，R = R' = SiMe34或Me 6，或R = H，R' = tBu 8或Ar 9；M = Y，R = R' = SiMe35，或R = H，R' = Ar 10）。描述了5的晶体结构。[Sc(NMe2)(N2NN')] 6与ArFNH2（ArF = C6F5）的σ-键置换反应得到了相应的一级氟苯甲酰胺衍生物7。将1或2与Li[PhC(NSiMe3)2]反应得到了动态的六配位苯甲酰亚胺衍生物[MPhC(NSiMe3)2}(N2NN')]（M = Sc 11或Y 12），报告了其晶体结构。最后，将1与LiCH2SiMe3反应形成了合理的产率的烷基衍生物[Sc(CH2SiMe3)(N2NN')] 13；描述了13的晶体结构。
• Post‐Metallocene Hydridolanthanide Chemistry: [Lu{(Me ₃ Si) ₂ NC(NiPr) ₂ } ₂ (μ‐H)] ₂ — A Novel Lanthanide Hydride in a Non‐Cyclopentadienyl Coordination Environment; Synthesis, Structure and Catalytic Activity in Olefin Polymerization
  作者：Alexander A. Trifonov、Elena A. Fedorova、Georgy K. Fukin、Mikhail N. Bochkarev

  DOI：10.1002/ejic.200400425

  日期：2004.11

  lithium guanidinate [Li(Me3Si)2NC(NiPr)2}], obtained in situ from the amide [LiN(SiMe3)2(Et2O)] and 1,3-diisopropylcarbodiimide in THF, yields the bis(guanidinate) “ate” complex [Lu(Me3Si)2NC(NiPr)2}2(μ-Cl)2Li(THF)2] (1). The alkyllutetium derivative [Lu(Me3Si)2NC(NiPr)2}2(CH2SiMe3)] (2) was synthesized by a metathesis reaction of 1 with LiCH2SiMe3 in toluene. The treatment of 2 with an equimolar amount

  无水 LuCl3 与两倍摩尔过量的胍酸锂 [Li(Me3Si)2NC(NiPr)2}] 的反应，由酰胺 [LiN(SiMe3)2(Et2O)] 和 1,3-二异丙基碳二亚胺原位获得THF，产生双（胍盐）“ate”复合物 [Lu(Me3Si)2NC(NiPr)2}2(μ-Cl)2Li(THF)2] (1)。烷基镥衍生物 [Lu(Me3Si)2NC(NiPr)2}2(CH2SiMe3)](2) 是通过 1 与 LiCH2SiMe3 在甲苯中的复分解反应合成的。在室温下用等摩尔量的 PhSiH3 在己烷中处理 2 导致第一个已知的二聚镧系元素氢化物在双（胍）配位环境中，[Lu(Me3Si)2NC(NiPr)2}2(μ-H) ]2 (3)。配合物 1 和 3 的晶体结构已通过 X 射线晶体学确定。发现氢化物络合物3催化乙烯、丙烯和苯乙烯的聚合。
• Chloro, Alkyl and Aryl Complexes of Rare Earth Metals Supported by Bulky Tetrasubstituted Guanidinate Ligands
  作者：Alexander A. Trifonov、Dmitrii M. Lyubov、Elena A. Fedorova、Georgy K. Fukin、Herbert Schumann、Stefan Mühle、Markus Hummert、Mikhail N. Bochkarev

  DOI：10.1002/ejic.200500641

  日期：2006.2

  the lithium guanidinate [Li(Et2O)][(Me3Si)2NC(NCy)2] afford the bis(guanidinate) “ate” complexes [(Me3Si)2NC(NCy)2]2Ln(μ-Cl)2Li(THF)2 [Ln = Y (5) and Lu (6)]. Treatment of 5 with dimethoxyethane results in the formation of [(Me3Si)2NC(NCy)2]2Y(μ-Cl)2Li(DME) (7). The carbyl complexes [(Me3Si)2NC(NCy)2]2Y-tBu] (8), [(Me3Si)2NC(NCy)2]2Y(μ-Me)2Li(TMEDA) (10) and [(Me3Si)2NC(NCy)2]2YPh(THF) (13) were obtained

  无水 LnCl3 (Ln = Y, Nd, Sm, Lu) 与两个当量的反应。N,N'-二环己基-N''-双(三甲基甲硅烷基)胍钠[(Me3Si)2NC(NCy)2]，得自Na[N(SiMe3)2]和1,3-二环己基取代的碳二亚胺CyN=C=NCy 在 THF 中，产生一氯双（胍）四氢呋喃络合物 [(Me3Si)2NC(NCy)2]2LnCl(THF) [Ln = Y (1), Nd (2), Sm (3) 和 Lu (4)]。YCl3 和 LuCl3 与胍酸锂 [Li(Et2O)][(Me3Si)2NC(NCy)2] 的类似反应得到双(胍)“ate”配合物 [(Me3Si)2NC(NCy)2]2Ln(μ -Cl)2Li(THF)2 [Ln = Y (5) 和 Lu (6)]。用二甲氧基乙烷处理 5 导致形成 [(Me3Si)2NC(NCy)2]2Y(μ-Cl)2Li(DME) (7)。羰基配合物
• Preparation of N,N,N′-tris(trimethylsilyl)amidines; a convenient route to unsubstituted amidines
  作者：René T. Boeré、Richard T. Oakley、Robert W. Reed

  DOI：10.1016/0022-328x(87)80017-7

  日期：1987.9

  The tris(trimethylsilyl)amidines RC(NSiMe3)N(SiMe3)2 (R  C6H5, p-CH3C6-H4, p-ClC6H4, p-MeOC6H4, p-Me2NC6H4, p-CF3C6H4, p-C6H5C6H4 and CF3) are prepared by the reaction of the respective nitriles with (Me3Si)2NLi·OEt2 in ether to give intermediates RC(NLi)N(SiMe3)2. Heating these intermediates with ClSiMe3 in toluene affords the products, which are isolated by vacuum distillation, in high yield. With

  三（三甲基甲硅烷基）am RC（NSiMe 3）N（SiMe 3）2（R C 6 H 5，p -CH 3 C 6 -H 4，p -ClC 6 H 4，p -MeOC 6 H 4，p -Me 2 NC 6 H 4，p -CF 3 C 6 H 4，p -C 6 H 5 C 6 H 4通过使各自的腈与（Me 3 Si）2 NLi·OEt 2在醚中反应，得到中间体RC（NLi）N（SiMe 3）2，制备CF 3和CF 3）。将这些中间体与在甲苯中的ClSiMe 3一起加热，以高收率得到产物，通过真空蒸馏将其分离。对于1，4-二氰基苯，两当量的试剂提供了全（三甲基甲硅烷基）-1，4-二m。用6 N乙醇HCl水解中间体，得到未取代的am盐酸盐RC（NH）NH 2 ·HCl（RC 6 -H 5，p -MeOCh 6 H4，对-ClC 6 H 4，对-O 2 NC 6 H 4）高收率。