CH[(CH3)2SiNH(p-tolyl)]3 | 156053-42-8

• 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: CH[(CH3)2SiNH(p-tolyl)]3
• 英文别名: HC[SiMe2NH(4-MeC6H4)]3；N-[bis[dimethyl-(4-methylanilino)silyl]methyl-dimethylsilyl]-4-methylaniline
• CAS: 156053-42-8
• 化学式: C₂₈H₄₃N₃Si₃
• 分子量: 505.926
• InChiKey: LARCWISOGZBVOD-UHFFFAOYSA-N

物化性质

• 沸点：
  553.5±50.0 °C(Predicted)
• 密度：
  1.028±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.31
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  36.1
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  CH[(CH3)2SiNH(p-tolyl)]3 以 乙醚 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  三齿三脚架三胺配体支持的第13组和镧系元素配合物：结构多样性和聚合催化

  摘要：

  由三齿三脚架三胺配体[N 3 ] H 3与新戊烷，三甲硅烷基甲烷或三甲硅烷基硅烷骨架和不同的N-取代基衍生而来的总共13种新颖的B，Al和Sm配合物的几种不同合成方法，以及它们的应用报道了选择的用于聚合催化的配合物。在Et 2 O /己烷中HC [SiMe 2 N（CH 2 Ph）] 3 Li 3（THF）2（THF =四氢呋喃）和AlCl 3之间的盐易位导致LiCl的完全消除和相应的三脚架三酰胺铝烷HC的形成[SiMe 2 N（CH 2Ph）] 3 Al·（THF）（1）。另一方面，{MeC [CHN（SiMe 3）] 3 Li 3 } 2和AlCl 3在Et 2 O /己烷中的反应产生含LiCl的化合物MeC [CH 2 N（SiMe 3）] 3 AlCl [ Li（Et 2 O）]（2）。涉及[N 3 ] H 3和1 AlMe 3的烷烃消除反应会生成二氨基氨基铝甲基HC [SiMe 2

  DOI：

  10.1021/om700587w
• 作为产物：
  描述：

  tris(bromodimethylsilyl)methane 、 乙烷,三氯氟- 在 三乙胺 作用下， 生成 CH[(CH3)2SiNH(p-tolyl)]3
  参考文献：
  名称：

  铀（IV）2三足的酰胺和卤化物衍生物三（Ñ -arylamido二甲基甲硅烷）甲烷†往最‡

  摘要：

  三当量ArNH 2（氩气= 3,5-Me 2 C 6 H 3）与HC（SiMe 2 Br）3在辅助碱NEt 3的存在下，以83％的产率提供了三脚架三（N-芳基胺-二甲基甲硅烷基）甲烷HC {SiMe 2 N（H）Ar} 3（1）。的三倍去质子化1与正丁基锂得到相应的三锂三（N-芳酰胺基-二甲基甲硅烷基）甲烷醚[HC {SiMe 2 N（Li）Ar} 3（OEt 2）]（2），产率为92％。盐2或已知配合物之间的消除反应[HC {SiMe 2 N（Li）Ar'} 3（OEt 2）2]（3）（氩气= 4-MeC 6 H 4），当量为四氯化铀得到相应的三（N-芳酰胺基-二甲基甲硅烷基）甲烷铀（IV）氯化物络合物作为单体[U（Cl）{HC（SiMe 2 NAr）3 }（THF）]（4）和双核[{HC（SiMe 2 NAr'）3 } U（Cl）（μ-Cl）U（THF）2 {（Ar'NSiMe 2）3

  DOI：

  10.1039/b926018h

文献信息

• Synthesis, structures, and alkene hydrosilation activities of neutral tripodal amidozirconium alkyls
  作者：Li Jia、Jiquan Zhao、Errun Ding、William W. Brennessel

  DOI：10.1039/b200789d

  日期：2002.6.27

  Aminolysis of Zr(CH2C6H5)4 with CH[(CH3)2SiNHAr]3 (Ar = para-tolyl and para-fluorophenyl) affords CH[(CH3)2SiNAr]3ZrCH2C6H51a and 1b (a: Ar = para-tolyl; b: Ar = para-fluorophenyl). Solution and solid state X-ray structural data suggest an η2-bonding mode for the benzyl group in 1a and 1b. Treating 1a and 1b with N,N-dimethylanilinium chloride or triphenylmethyl chloride yields CH[(CH3)2SiNAr]3ZrCl (2a and 2b). Complex 2a exhibits a fast dimer–monomer equilibrium in benzene. Single-crystal X-ray diffraction of 2a reveals a dimeric structure bridged by two μ-Cl atoms. Metathesis of 2a and 2b with n-butyllithium in toluene and then in hexane yields CH[(CH3)2SiNAr]3ZrnBu (3a and 3b). The crystal structures and the IR spectra of 3a and 3b in Nujol mulls reveal weak β-agostic interactions, but solution NMR spectra of 3a and 3b give no evidence for such a motif. Further, the larger Zr–Cα–Cβ angles and the longer Zr–Cβ distances suggest the β-agostic interactions in 3a and 3b are weaker than those in the previously reported cases of Group 4 metals. Complexes 1a, 1b, 3a, and 3b are active alkene hydrosilation catalysts. The catalytic activities exhibited by these complexes are in contrast to the inertness of the previously reported neutral molecules of the type X3MR (X = amide, alkoxide, or siloxide; M = Group 4 metal; R = alkyl or hydride). We attribute the improved activity to three factors: the small ancillary groups of the ligand, the accessibility of the coordination sites cis to the Zr-alkyl group due to the small “bite angle” of the ligand, and the weakened N(p) → Zr(d) π donation due to the coordination geometry imposed by the tripodal ligand.

  Zr(CH2C6H5)4 与 CH[(CH3)2SiNHAr]3（Ar=对位甲苯基和对位氟苯基）发生氨解反应，得到 CH[(CH3)2SiNAr]3ZrCH2C6H51a 和 1b（a：Ar=对位甲苯基；b：Ar=对位氟苯基）。溶液和固态 X 射线结构数据表明，1a 和 1b 中的苄基具有 η2 键合模式。将 1a 和 1b 与 N,N-二甲基氯化萘或三苯基甲基氯化萘处理，可得到 CH[(CH3)2SiNAr]3ZrCl （2a 和 2b）。络合物 2a 在苯中表现出快速的二聚体-单体平衡。2a 的单晶 X 射线衍射显示出由两个 μ-Cl 原子桥接的二聚体结构。2a 和 2b 与正丁基锂在甲苯中进行 Metathesis 反应，然后在己烷中进行 Metathesis 反应，得到 CH[(CH3)2SiNAr]3ZrnBu （3a 和 3b）。3a 和 3b 在 Nujol 茂金属中的晶体结构和红外光谱显示出微弱的 β-ostic 相互作用，但 3a 和 3b 的溶液核磁共振光谱没有显示出这种作用。 此外，较大的 Zr-Cα-Cβ 角和较长的 Zr-Cβ 间距表明 3a 和 3b 中的β-ostic 相互作用比之前报告的第 4 族金属中的作用要弱。络合物 1a、1b、3a 和 3b 是活跃的烯烃加氢催化剂。这些络合物表现出的催化活性与之前报道的 X3MR 型中性分子（X = 酰胺、烷氧化物或硅氧化物；M = 第 4 族金属；R = 烷基或氢化物）的惰性形成了鲜明对比。我们将活性的提高归因于三个因素：配体的附属基团较小；由于配体的 "咬合角 "较小，Zr-烷基的顺式配位位点容易接近；由于三足配体的配位几何形状，N(p) → Zr(d) π 的捐赠减弱。
• Tripodal Amido Boron and Aluminum Complexes
  作者：Hongping Zhu、Eugene Y.-X. Chen

  DOI：10.1021/ic0620889

  日期：2007.2.19

  structural elucidations of novel boron and aluminum complexes incorporating the tripodal triamido [N3]3- ligand framework that is hypothesized to promote the preorganized pyramidal geometry for high Lewis acidity are reported. Salt metathesis between the in situ-generated trianionic lithium complexes of the tripodal amido ligands with BCl3 leads to boranes HC[SiMe2N(4-MeC6H4)]3B (1) and MeSi[SiMe2N(4-MeC6H4)]3B

  据报道，结合了三脚架三酰胺[N3] 3-配体骨架的新型硼和铝配合物的合成和结构阐明，据推测该骨架可促进高路易斯酸度的预组织锥体几何结构。三脚架氨基配体与BCl3的原位生成的三阴离子锂配合物之间的盐复分解反应生成硼烷HC [SiMe2N（4-MeC6H4）] 3B（1）和MeSi [SiMe2N（4-MeC6H4）] 3B（2）；然而，用笨重的tBu取代N-Ar基团可通过明显消除MeBCl2产生意想不到的不含硼的LiCl加合物[HC（SiMe2NtBu）2（SiMeNtBu）] Li3（Et2O）Cl} 2（3）。由AlCl3与盐复分解反应衍生的产物由反应介质确定：在己烷-乙醚混合物或甲苯中进行反应时，得到溶剂化的盐加合物HC [SiMe2N（4-MeC6H4）] 3Al。ClLi（Et2O）2（4）或盐加合物HC [SiMe2N（4-MeC6H4）] 3Al.ClLi（5）；加入少量四氢呋喃可生成HC
• First structural characterization of a mixed valent thallium(i/iii) amide bearing an n-butylthallium(iii) unit stabilized by a tripodal amido ligand
  作者：Christian H. Galka、Lutz H. Gade

  DOI：10.1039/b100760m

  日期：——

  Lithiation of the tripodal amine HCSiMe2NH(p-Tol)}3 with BunLi in the presence of TlCl yielded the Tl(I/III) mixed valent complex [HCSiMe2N(p-Tol)}3(TlBun )(Tl)] 2; an X-ray diffraction study established the central n-butyl–thallium(III) unit coordinated by the amido tripod in which two of the amido functions are additionally bridged by the Tl(I) atom.

  三元胺 HCSiMe2NH(p-Tol)}3 与 BunLi 在 TlCl 存在下发生锂化反应，生成了 Tl(I/III)混合价配合物 [HCSiMe2N(p-Tol)}3(TlBun )(Tl)] 2；X 射线衍射研究确定了中央正丁基铊(III)单元由氨基三元胺配位，其中两个氨基功能由 Tl(I)原子额外桥接。
• Hellmann, Konrad W.; Friedrich, Stefan; Gade, Lutz H., Chemische Berichte, 1995, vol. 128, # 1, p. 29 - 34
  作者：Hellmann, Konrad W.、Friedrich, Stefan、Gade, Lutz H.、Li, Wan-Sheung、McPartlin, Mary

  DOI：——

  日期：——
• Tripodal Triamidostannates and -plumbates
  作者：Konrad W. Hellmann、Lutz H. Gade、Olaf Gevert、Paul Steinert、Joseph W. Lauher

  DOI：10.1021/ic00120a010

  日期：1995.8

  Reaction of the tripodal trilithium amides HCSiMe(2)N(Li)(4-CH3C6H4)}(3)(THF)(2) (1) and CH3SiSiMe(2)N(Li)-(tBu)(3)(THF)(x) with SnCl2 or Cp(2)Pb gave the corresponding lithium triamidostannates and -plumbates HCSiMe(2)N(4-CH3C6H4)}3SnLi(THF)(3) (2), [HCSiMe(2)N(4-CH3C6H4)}Pb-3][Li(THF)(4)] (4), and CH3SiSiMe(2)N(tBu)}(3-)MLi(THF) (M = Sn: 7; Pb: 8). The X-ray structure analysis of 2 revealed molecular as well as crystallographic 3-fold symmetry and established a short direct Li-Sn contact [d(av)(Sn-Li) = 2.93(5); two independent molecules in the unit cell]. 2: hexagonal, P6(3) (No. 173), alpha = 15.664(4) Angstrom, c = 22.421(11) Angstrom, Z = 4, V = 4765(3) Angstrom(3), R = 0.038. An X-ray structure analysis of 8 established direct bonding of the (THF)Li counterion to two N-functions of the triamido metalate unit in a bridging fashion, a situation that, as the NMR spectra show, pertains in solution. 8: orthorhombic, Pbca (No. 61), alpha = 10.8201(2) Angstrom, b = 20.0825(3) Angstrom, c = 31.5806(3) Angstrom, Z= 8, V= 6862.3(3) Angstrom(3), R = 0.076. If two molar equivalents of MeN(CH(2)CH(2)NMe(2))(2) are added to the in situ generated 2 the ''solvent separated'' ion pair [MeN(CH(2)CH(2)NMe(2))(2)Li},Cl][HCSiMe(2)N(4-CH3C6H4)}Sn-3] (5) is formed, which contains a solvated Li2Cl](+) cation. Crystal data of 5 as established in an X-ray structure analysis: triclinic, P-l (No. 2), alpha = 12.377(2) Angstrom, b = 15.360(2) Angstrom, c = 17.594(3) Angstrom, alpha = 77.41(1)degrees, beta = 74.16(2)degrees, gamma = 70.94(3)degrees, Z = 2, V= 3011.2 Angstrom(3), R = 0.072. While reaction of H3CCN(Li)SiMe(3)}(3)(THF)(3) With SnCl2 gives the corresponding stannate H3CC(NSiMe(3))(3)SnLi(THF) which on the basis of its spectroscopic data is thought to have a similar structure to 7 and 8, the analogous plumbate could be isolated neither from the reaction with Cp(2)Pb nor with PbCl2. The latter showed marked redox reactivity effecting fragmentation of the ligand. From the reaction mixture of this system a crystalline solid was isolated in ca. 25% yield. This was identified by elemental analysis and X-ray structure analysis as [H3CC(CH(2)NSiMe(3))(2)(CH2O(Li))Pb](2) (11) which has a fused cage structure. 11: triclinic, Pi (No. 2), alpha = 8.4889(2) Angstrom, b = 11.1832(4) Angstrom, c = 11.7308(3) Angstrom, alpha = 62.010(5)degrees, beta = 71.163(4)degrees, gamma 68.528(5)degrees, Z = 2, V = 899.5(2) Angstrom(3), R = 0.054.