[Li(N(2,4,6-tris[bis(trimethylsilyl)methyl]phenyl)C(Me)CHC(Me)N(2,4,6-trimethylphenyl))] | 676321-94-1

• 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: [Li(N(2,4,6-tris[bis(trimethylsilyl)methyl]phenyl)C(Me)CHC(Me)N(2,4,6-trimethylphenyl))]
• 英文别名: Li(N(2,4,6-tris[bis(trimethylsilyl)methyl]phenyl)C(Me)CHC(Me)N(2,4,6-trimethylsilyl))；[Li(nacnac)]
• CAS: 676321-94-1
• 化学式: C₄₁H₇₇LiN₂Si₆
• 分子量: 773.53
• InChiKey: GZNDJUAJOZWMIJ-QRMJEXOFSA-N

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：

  氯化铪(IV)四氢呋喃络合物 、 [Li(N(2,4,6-tris[bis(trimethylsilyl)methyl]phenyl)C(Me)CHC(Me)N(2,4,6-trimethylphenyl))] 在 KC₈ 作用下， 以 苯 为溶剂， 以82%的产率得到[Hf=N(2,4,6-tris[bis(trimethylsilyl)methyl]phenyl)(C(Me)CHC(Me)N(2,4,6-trimethylphenyl))Cl(thf)]
  参考文献：
  名称：

  Reduction of Tetravalent Group 4 Metal Complexes Supported by an Extremely Bulky, Unsymmetrically Substituted β-Diketiminato Ligand Leading to the Regioselective CN Bond Cleavage Giving Ring-Contracted Metal-Imido Complexes

  摘要：

  Reductions of tetravalent group 4 metal beta-diketiminates, [(MCl3)-Cl-IV(nacnac)(thf)(n)] (2a, M = Ti; 3b, M = Zr; 3c, M = Hf; nacnac = {N(Tbt)C(Me)CHC(Me)N(Mes)}(-), Tbt = 2,4,6-tris[bis(trimethylsilyl)-methyl]phenyl, Mes = 2,4,6-trimethylphenyl, n = 0, 1), with 2 equiv of KC8 in the presence of LiCl and tmeda afforded the metal-imido complexes [M=NTbt{C(Me)CHC(Me)N(Mes)}(mu-Cl)(2)Li(tmeda)] (4a, M = Ti; 4b, M = Zr; 4c, M = Hf; tmeda = Me2NCH2CH2NMe2). The formation of imido complexes 4a-c can be explained in terms of the generation of the corresponding divalent complexes [(MCl)-Cl-II(nacnac)(L)(n)] (6a, M = Ti; 6b, M = Zr; 6c, M = Hf; L = thf or Li(tmeda), etc.), followed by the reductive, regioselective cleavage of the C=N bond tethered to the Tbt group. The intermediacy of the divalent titanium complex 6a was supported by the alternative formation of 4a in the reaction of [Li(nacnac)] (1) with [(TiCl2)-Cl-II(tmeda)(2)](-) Interestingly, 4a-c reacted with H2O to give the free ligand nacnacH (8).

  DOI：

  10.1021/om0509948

文献信息

• Nucleophilic Attack toward Group 4 Metal Complexes Bearing Reactive 1-Aza-1,3-butadienyl and Imido Moieties
  作者：Hirofumi Hamaki、Nobuhiro Takeda、Norihiro Tokitoh

  DOI：10.1021/ic0620844

  日期：2007.3.1

  electrophilicity of 2a at the carbon atom connecting to the titanium atom. Interestingly, the reaction of zirconium and hafnium analogues (2b and 2c) with PMe3 and dmpe did not proceed. In contrast to the cases of phosphine reagents, pyridine which was found to undergo the nucleophilic attack toward the titanium center of 2a gave the pyridine-coordinated titanium-imide [Ti=NTbtC(Me)CHC(Me)N(Mes)}Cl(py)]

  带有bearing叶立德部分[Ti = NTbt C（Me）（PR3）CH = C（Me）N（Mes）} Cl]的独特（1-氮杂-2-丁烯基）钛配合物（3-5，Tbt = 2通过PMe3，P（n-Bu）3和1,2-双（二甲基膦基）的亲核攻击形成了4,4,6-三[双（三甲基硅烷基）甲基]苯基，Mes = 2,4,6-三甲基苯基）乙烷（dmpe）朝向相应的（1-氮杂-1,3-丁二烯基）钛配合物[Ti = NTbt C（Me）CHC（Me）N（Mes）}（mu-Cl）2Li（tmeda）] （2a）。β-二酮化锂[Li N（Tbt）C（Me）CHC（Me）N（Mes）}]（1）与[TiIICl2（dmpe）2]的反应也导致形成相同的络合物5.密度泛函理论计算表明，模型分子3的负电荷稍微离域到C3N平面。此外，对2a模型分子的计算表明，2a在与钛原子连接的碳原子上具有亲电性。有趣的是，锆和h