<α-(trimethylsilyl)benzyl>lithium N,N,N'N'-tetramethylethylenediamne complex | 105034-70-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: <α-(trimethylsilyl)benzyl>lithium N,N,N'N'-tetramethylethylenediamne complex
• 英文别名: α-(trimethylsilyl)benzyllithium * tetramethylenediamine；Li{CH(SiMe3)Ph}(tmeda)
• CAS: 105034-70-6
• 化学式: C₆H₁₆N₂*C₁₀H₁₅Si*Li
• 分子量: 286.462
• InChiKey: CUVFIJVCVRQPRE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.88
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  6.48
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  <α-(trimethylsilyl)benzyl>lithium N,N,N'N'-tetramethylethylenediamne complex 、 [U(C(P(phenyl)₂NSi(methyl)₃)₂)(Cl)(μ-Cl)₂Li(tetrahydrofuran)₂] 以 甲苯 为溶剂， 反应 3.5h， 生成
  参考文献：
  名称：

  铀的甲硅烷基-膦-碳烯络合物（IV）

  摘要：

  介绍了前所未有的铀（IV）的甲硅烷基-膦-卡宾配合物，在此之前，所有共价act-碳双键都被磷（V）取代基稳定化或仅限于基质分离实验。将[U（BIPM TMS）（Cl-（μ‐Cl）2 Li（THF）2 ]（1，BIPM TMS = C（PPh 2 NSiMe 3）2）转换为[U（BIPM TMS）（Cl）{CH （Ph）（SiMe 3）}]（2）和[Li {CH {SiMe 3）（PPh 2）}（THF）] / Me 2 NCH 2 CH 2 NMe 2的添加（TMEDA）通过α-氢提取得到[U {C（SiMe 3）（PPh 2）}（BIPM TMS）（μ-Cl）Li（TMEDA）（μ-TMEDA）0.5 ] 2（3）。2,2,2-穴状配体或4-N，N-二甲氨基吡啶（DMAP），以两个当量的另外3，得到[∪{C（森达3）（PPH 2）} ...（BIPM TMS）（CL）] [李（ 2,2,2-cryptand）]（4）或[U

  DOI：

  10.1002/anie.201802080
• 作为产物：
  描述：

  苄基三甲基硅烷 在 正丁基锂 、 四甲基乙二胺 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 <α-(trimethylsilyl)benzyl>lithium N,N,N'N'-tetramethylethylenediamne complex
  参考文献：
  名称：

  Zarges, Wolfgang; Marsch, Michael; Harms, Klaus, Chemische Berichte, 1991, vol. 124, # 3, p. 543 - 549

  摘要：

  DOI：

文献信息

• The reactions of lithium trimethysilylmethyls with isocyanides; structures and reactions of the derived lithium 1-azaallyls, β-diketiminates and a 1-azabuta-1,3-dienyl-3-amide
  作者：Peter B. Hitchcock、Michael F. Lappert、Marcus Layh

  DOI：10.1039/b103553n

  日期：——

  The insertion of ArNC (Ar = 2,6-Me2C6H3) or ButNC into the Li–C bond of [LiC(H)(R)R′}] (R = SiMe3, R′ = R or Ph) led to (i) the lithium 1-azaallyls [LiN(R″)C(R)C(H)R′}(tmen)] (6a R′ = R, R″ = Ar; 6b R′ = Ph, R″ = Ar; 6c R′ = Ph, R″ = But), (ii) the lithium β-diketiminates [LiN(But)C(R)C(H)C(R)NBut}][(LiCHR2)(CNBut)] 1, LiN(Ar)C(R)C(H)C(R)N(Ar)} 2 and [LiN(Ar)C(R)C(H)C(Ph)N(R)}(tmen)] 7 (from 6a and PhCN), or (iii) the lithium amide [LiN(Ar)C(R)C[N(Ar)]C(H)Ph}(tmen)] 8. Treatment of the lithium β-diketiminates 1 and 2 with ZrCl4 yielded the complexes [ZrCl3N(But)C(R)C(H)C(R)NBut}] 3 or [ZrN(Ar)C(R)C(H)C(R)N(Ar)}Cl2(μ-Cl)2Li(OEt2)2] 4, while reaction of the lithium compounds 2 or 8 with MeOH gave in high yield the conjugate acids of the corresponding anions [HN(Ar)C(R)C(H)C(R)NAr] 5 or [HN(Ar)C(R)CN(Ar)}C(H)Ph] 9. Each of the compounds 1–9 was fully characterised by multinuclear NMR spectroscopy, mass spectrometry and microanalysis, while X-ray diffraction data are also provided for the complexes 4, 6b and 8.

  将 ArNC（Ar = 2,6-Me2C6H3）或 ButNC 插入[LiC(H)(R)Râ²}]（R = SiMe3，Râ²Â = R 或 Ph）的 LiâC 键导致 (i) 1-氮杂烯丙基锂[LiN(Râ³)C(R)C(H)Râ²}(tmen)]（6a Râ²Â = R，Râ³Â = Ar；6b Râ²Â = Ph, Râ³Â = Ar；6c Râ²Â = Ph, Râ³Â = But），(ii) δ-二酮酸锂[LiN(But)C(R)C(H)C(R)NBut}][(LiCHR2)(CNBut)] 1、LiN(Ar)C(R)C(H)C(R)N(Ar)} 2 和 [LiN(Ar)C(R)C(H)C(Ph)N(R)}(tmen)] 7（由 6a 和 PhCN 制得），或 (iii) 锂酰胺 [LiN(Ar)C(R)C[N(Ar)]C(H)Ph}(tmen)] 8。8.用 ZrCl4 处理δ-二酮亚胺锂 1 和 2，可得到络合物 [ZrCl3N(But)C(R)C(H)C(R)NBut}] 3 或 [ZrN(Ar)C(R)C(H)C(R)N(Ar)}Cl2(δ-Cl)2Li(OEt2)2] 4、而将锂化合物 2 或 8 与 MeOH 反应，可以高产率地得到相应阴离子的共轭酸 [HN(Ar)C(R)C(H)C(R)C(R)NAr] 5 或 [HN(Ar)C(R)CN(Ar)}C(H)Ph] 9。每种化合物 1â9 都通过多核核磁共振光谱、质谱和显微分析进行了全面表征，同时还提供了复合物 4、6b 和 8 的 X 射线衍射数据。
• Reactions of LiCHR2 and related lithium alkyls with α-H free nitriles and the crystal structures of eleven representative lithium 1,3-diazaallyls, 1-azaallyls and β-diketiminates
  作者：Peter B. Hitchcock、Michael F. Lappert、Marcus Layh、Dian-Sheng Liu、Rafael Sablong、Tian Shun

  DOI：10.1039/b002376k

  日期：——

  Reactions between bis(trimethylsilyl)methyllithium LiCHR2 and a nitrile R′CN gave lithium 1-azaallyls, β-diketiminates or 1,3-diazaallyls. The products of related processes involving the lithium alkyl LiCH2R, LiCH(R)Ph or [Li(tmen)]2[1,2-C(H)R}2C6H4] have also been obtained (R = SiMe3 and R′ = But, Ph or C6H4Me-4). Analytical and spectroscopic data served to identify the following crystalline compounds: [LiN(R)C(But)C(H)R}(D)]n [D absent and n = 2; D = tmen or dme and n = 1], [LiN(R)C(Ph)C(H)R}(D)]n [D = tmen or pmdien and n = 1, or D = thf and n = 2], [LiN(R)C(Ph)C(H)C(R′′)NR}(D)]n [D absent, n = 2 and R′′ = Ph (4a), C6H4Me-4 (4b) or But; or D = tmen, (thf)2 (9b), NEt3 or thf and NCPh and n = 1 and R′′ = Ph], [LiN(R)C(Ph)C(H)C(Ph)NR}(D)Li(CHR2)] [D = OEt2 or thf], [LiN(R)C(Ar)NC(Ph)C(H)R}(D)]n [D = tmen, n = 1 and Ar = Ph or C6H4Me-4; or D = thf, n = 2 and Ar = Ph], [LiN(Ph)C(R)NC(Ph)C(H)R}(tmen)], [LiN(R)C(But)CH2]2, [LiN(R)C(Ph)C(H)Ph}(tmen)], and [Li(tmen)]2[1,2-N(R)C(But)CH}2C6H4]. Each of the three classes of ligands has a diversity of ligating possibilities, functioning towards lithium variously in a terminal or bridging and mono- or bi-dentate fashion, the role of a neutral donor D often being crucial. For an isomeric pair, the lithium β-diketiminate was thermodynamically preferred over the 1,3-diazaallyl. From [LiN(R)C(But)C(H)R}]2 and successively CH2Br2 and LiBun, the further lithium 1-azaallyl compound [LiN(R)C(But)C(H)C(H)(R)Bun}]2 was obtained. From 4a and CH2Br2 or (BrCH2)2 a bis(β-diketiminyl)methane CH2[CC(Ph)NR}C(Ph)N(H)R]2 or 9b or β-diketimine HN(R)C(Ph)C(H)C(Ph)NR were obtained, while 4b with successively KOBut and H2O gave the β-diketimine HN(R)C(C6H4Me-4)C(H)C(C6H4Me-4)NR. Mechanistic pathways are proposed, which involve Me3Si migrations: from C to N or N to N; or, for the latter a 1,2-dyotropic Me3Si/H exchange. The crystal structures of eleven of these compounds have been determined. Each of the new lithium compounds may in principle behave as an N-, C-, (N,N′)-, or (N,C)-centred nucleophile. Reactions demonstrating the first two alternatives for the β-diketiminate [LiN(R)C(Ar)C(H)C(Ar)NR}]2 are (i) those with water (Ar = C6H4Me-4) or (BrCH2)2 (Ar = Ph) which gave the diketimine N(R)C(Ar)C(H)C(Ar)N(H)R, whereas (ii) that with CH2Br2 (Ar = Ph) yielded CH2[CC(Ph)NR}C(Ph)N(H)R]2.

  双（三甲基硅基）甲基锂 LiCHR2 与腈（Râ²CN）发生反应，生成 1-氮杂烯丙基锂、δ-二缩酮或 1,3-二氮杂烯丙基锂。在涉及烷基锂 LiCH2R、LiCH(R)Ph 或 [Li(tmen)]2[1,2-C(H)R}2C6H4]的相关过程中也得到了产物（R = SiMe3，Râ²Â = But、Ph 或 C6H4Me-4）。分析和光谱数据有助于确定以下晶体化合物：[LiN(R)C(But)C(H)R}(D)]n [D缺席，n = 2；D = tmen 或 dme 且 n = 1]，[LiN(R)C(Ph)C(H)R}(D)]n [D = tmen 或 pmdien 且 n = 1，或 D = thf 且 n = 2]、[LiN(R)C(Ph)C(H)C(Râ²â²)NR}(D)]n [D 缺席，n = 2 和 Râ²â²Â = Ph (4a)，C6H4Me-4 (4b) 或 But；或 D = tmen、(thf)2 (9b)、NEt3 或 thf 和 NCPh，n = 1，Râ²â²Â = Ph]、[LiN(R)C(Ph)C(H)C(Ph)NR}(D)Li(CHR2)] [D = OEt2 或 thf]，[LiN(R)C(Ar)NC(Ph)C(H)R}(D)]n [D = tmen，n = 1 和 Ar = Ph 或 C6H4Me-4；或 D = thf，n = 2 和 Ar = Ph]、[LiN(Ph)C(R)NC(Ph)C(H)R}(tmen)]、[LiN(R)C(But)CH2]2、[LiN(R)C(Ph)C(H)Ph}(tmen)]和 [Li(tmen)]2[1,2-N(R)C(But)CH}2C6H4]。这三类配体中的每一类都有多种配位可能性，对锂的作用方式各不相同，有末端配位或桥接配位，单齿配位或双齿配位，中性供体 D 的作用往往至关重要。对于一对异构体来说，δ-二乙二酸锂在热力学上比 1,3-二氮杂烯丙基锂更受青睐。从[LiN(R)C(But)C(H)R}]2 和 CH2Br2 以及 LiBun 相继得到 1-氮杂烯丙基锂化合物 [LiN(R)C(But)C(H)C(H)(R)Bun}]2。从 4a 和 或 (BrCH2)2 得到双(δ-二酮亚氨基)甲烷 CH2[CC(Ph)NR}C(Ph)N(H)R]2 或 9b 或 δ-二酮亚氨基 HN(R)C(Ph)C(H)C(Ph)NR、而 4b 与 KOBut 和 H2O 相继反应后得到了δ-二酮亚胺 HN(R)C(C6H4Me-4)C(H)C(C6H4Me-4)NR。提出的机理途径涉及 Me3Si 迁移：从 C 迁移到 N 或从 N 迁移到 N；或者，后者是 1,2 向性 Me3Si/H 交换。其中 11 种化合物的晶体结构已经确定。原则上，每种新锂化合物都可以表现为以 N、C、(N,Nâ²)或 (N,C) 为中心的亲核体。证明δ-二酮亚胺[LiN(R)C(Ar)C(H)C(Ar)NR}]2 的前两种选择的反应是：(i) 与水 (Ar = C6H4Me-4)或 (BrCH2)2 (Ar = Ph) 的反应，得到二酮亚胺 N(R)C(Ar)C(H)C(Ar)N(H)R、而(ii) （Ar = PhÂ）则生成 CH2[CC(Ph)NR}C(Ph)N(H)R]2。
• Synthesis and Characterization of Substituted Benzyl Zinc Derivatives ‐ Molecular Structures of (tmeda) Li‐CH (GeMe ₃ )Ph, (tmeda)Zn(CH ₂ Ph) ₂ , (tmeda)Zn[CH(SiMe ₃ )Ph] ₂ , and (tmeda)Zn[CH(SiMe ₃ )Ph]N(H)Si(SiMe ₃ ) ₃
  作者：Matthias Westerhausen、Michael Wieneke、Bernd B. Rademacher、Wolfgang Schwarz

  DOI：10.1002/cber.19971301024

  日期：1997.10

  chloride-tmeda with lithium tris(trimethylsilyl)silylamide allows the isolation of the corresponding heteroleptic tmeda complex of an alkylzinc amide. The metalation of phenyl(trimethylstannyl)methane with butyllithium yields the transmetalation product benzyllithium. From the metathesis reaction of this lithium base with anhydrous zinc(II) chloride in the presence of tmeda, the tmeda adduct of dibenzylzinc crystallizes

  在tmeda存在下，苯基（三甲基甲硅烷基）甲烷化锂与苯基（三甲基甲硅烷基）甲基氯化锌-tmeda的反应生成加成产物双（tmeda）-二烷基氯锌酸锂。氯化锂的消除导致双[苯基-（三甲基甲硅烷基）甲基]锌的tmeda加合物的形成。苯基（三甲基甲硅烷基）甲基氯化锌-tmeda与三（三甲基甲硅烷基）甲硅烷基氨基锂的易位反应使得可以分离烷基锌酰胺的相应杂配的tmeda配合物。苯基（三甲基锡烷基）甲烷与丁基锂的金属化反应产生了过渡金属化产物苄基锂。在tmeda存在下，由该锂碱与无水氯化锌（II）的复分解反应，使二苄基锌的tmeda加合物结晶。（tmeda）LiCH（GeMe）的分子结构3）Ph，（tmeda）Zn（CH 2 Ph）2，（tmeda）Zn [CH（SiMe 3）Ph] 2和（tmeda）Zn [CH（SiMe 3）-Ph [N（H）Si（SiMe）3）3个报告。而在一个η锂键3 -时尚，
• Synthesis and Structures of Solvent-Separated Lithium Zincates of the Type [Li(tmeda)₂]⁺[Me₃_-<i>_n</i>Zn{CH(SiMe₃)Ph}<i>_n</i>]^- (<i>n</i> = 1−3, tmeda = 1,2-Bis(dimethylamino)ethane)
  作者：Matthias Westerhausen、Michael Wieneke、Werner Ponikwar、Heinrich Nöth、Wolfgang Schwarz

  DOI：10.1021/om971092c

  日期：1998.3.1

  the tmeda complex of ((trimethylsilyl)benzyl)zinc chloride in the presence of 1,2-bis(dimethylamino)ethane (tmeda) in 2:1 molar ratio quantitatively yields the heteroleptic zincate [Li(tmeda)2]+[Me3-nZnCH(SiMe3}Ph]n]- (n = 1, 1). Under similar conditions, MeLi and ((trimethylsilyl)benzyl)lithium react with bis((trimethylsilyl)benzyl)zinc to form the zincates with n = 2 (2) and 3 (3), respectively. The

  甲基锂与（（三甲基甲硅烷基）苄基）氯化锌的tmeda络合物在1,2-双（二甲基氨基）乙烷（tmeda）的摩尔比为2：1的反应中定量生成杂合锌酸盐[Li（tmeda）2 ] + [Me 3 - n Zn CH（SiMe 3 } Ph] n ] -（n = 1，1）。在相似的条件下，MeLi和（（三甲基硅烷基）苄基）锂与双（（三甲基硅烷基）苄基）锌反应分别形成n = 2（2）和3（3）的锌酸盐。1和2的分子结构 与甲基取代基相比，与甲基取代的Zn-C键的长度更短。
• 1,2-bis(dimethylamino) ethan-komplexe von heteroleptischen alkylzink-verbindungen: Zusammenhang zwischen ZnN-abstand und RZnR′-bindungswinkel
  作者：Matthias Westerhausen、Michael Wieneke、Wolfgang Schwarz

  DOI：10.1016/0022-328x(96)06207-9

  日期：1996.9

  The synthesis and isolation of heteroleptic diorganylzinc compounds enforces the use of either sterically demanding substituents or the formation of a tmeda complex. The occupation of the coordination sites at the zinc atom prevents the dismutation to the homoleptic derivatives. These tmeda adducts show a linear dependency of the RZnR′ bond angle and the ZnN distance, which is discussed in detail

  杂合二有机基锌化合物的合成和分离可强制使用空间要求的取代基或形成tmeda配合物。锌原子上配位位点的占据防止了向均配衍生物的歧化。这些tmeda加合物显示了RZnR'键角和ZnN距离的线性相关性，将在两个示例中详细讨论。对于[1,2-双（二甲基氨基）乙烷-N，N']氯化锌苯基（三甲基甲硅烷基）甲烷（三斜硅烷基），观察到ZnN键长为215 pm，CZnCl角为122.2° ，而氯取代基被甲基取代（三斜链，）导致ZnN键长为224 pm，且CZnC角加宽为131.1°。线性关系的外推法预测线性RZnR'部分的ZnN距离为290 pm，键长为109°的键长为190 pm。该最后提及的值对应于ZnN单键，例如在杂配的三（三甲基甲硅烷基）甲基锌双（三甲基甲硅烷基）酰胺中（单斜晶系，P 2 1 / n，a = 904.74（7），b = 1668.72） （9），c = 1806