Li(N=CtBuPh) | 54655-19-5

• 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=CtBuPh)
• 英文别名: lithium;(2,2-dimethyl-1-phenylpropylidene)azanide
• CAS: 54655-19-5
• 化学式: C₁₁H₁₄LiN
• 分子量: 167.18
• InChiKey: KSCAZARIDXGLCX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  三氯一茂钛 、 Li(N=CtBuPh) 以 甲苯 为溶剂， 以88%的产率得到
  参考文献：
  名称：

  酮亚胺配体对（环戊二烯基）（酮亚胺）钛配合物-MAO催化剂体系催化乙烯聚合和乙烯/降冰片烯共聚的影响：Cp * TiCl 2（N CPh 2）

  摘要：

  配体对乙烯聚合和乙烯/ NBE共聚合的催化活性[和降冰片烯（NBE）的掺入]的影响，使用含Cp'TiCl 2 [ Kn （R 1）R] 2 ] [Cp'= Cp（1），C 5 Me 5（Cp ∗，2）; 研究了R 1，R 2  =  t Bu，t Bu（a），t Bu，Ph（b），Ph，Ph（c）]-甲基铝氧烷（MAO）催化剂体系。CpTiCl 2制备并鉴定了[NC（t Bu）Ph]（1b）CpTiCl 2（NCPh 2）（1c）和Cp ∗ TiCl 2（NCPh 2）（2c）。通过X射线晶体学确定Cp * TiCl 2（NCPh 2）（2c）的结构。乙烯聚合的催化活性按以下顺序增加：1a  >  1b  >  1c，这表明酮亚胺基配体的电子性质会影响活性。但是，通过以下方法制得的所得（共）聚合物的分子量分布1b，c和2c -MAO催化剂体系是双峰或多峰的，这表明酮亚胺取代基起关键作用，以

  DOI：

  10.1016/j.jorganchem.2007.04.043
• 作为产物：
  描述：

  [Li]₂[Ce(N=C^tBuPh)₆] 以 氘代四氢呋喃 为溶剂， 生成 [Li][Ce(N=C^tBuPh)₅] 、 Li(N=CtBuPh)
  参考文献：
  名称：

  合成，表征，和均配型F元素酮酰亚胺配合物的电化学[李] 2 [M（N = C吨BUPH）6 ]（M =铈，钍）

  摘要：

  [CE（NO的反应3）3（THF）4 ]与6当量的Li（N = C的吨BUPH），随后加入0.5当量的我的2，得到均配型的Ce（IV）酮酰亚胺[李] 2 [ CE（N = C吨BUPH）6 ]（1），其可在44％分离后处理后的产率。类似地，反应[ThCl 4（DME）2 ]（DME = 1,2-二甲氧基乙烷）与Li（N = C的6当量吨的四氢呋喃，得到BUPH）同构钍（Ⅳ）酮酰亚胺[李] 2 [钍（ N = C吨BUPH）6 ]（2），后处理后可以将其分离为53％的收率。既1和2进行了充分表征，包括X射线晶体学分析，从而允许一个详细的结构和光谱比较。还利用密度泛函理论和多构型波函数计算探索了1和2的电子结构。此外，通过循环伏安法探测了1的氧化还原化学反应，揭示了高阴极Ce（IV）/ Ce（III）还原电位，为酮亚胺基配体稳定镧系元素高氧化态的能力提供了证据。

  DOI：

  10.1021/acs.inorgchem.9b01428

文献信息

• Synthesis of zirconocene amides and ketimides and an investigation into their ethylene polymerization activity
  作者：Kenneth W Henderson、Amanda Hind、Alan R Kennedy、Arlene E McKeown、Robert E Mulvey

  DOI：10.1016/s0022-328x(02)01559-0

  日期：2002.8

  The zirconocene amide [Cp2Zr(Cl)N(CH2Ph)2] (5), and the zirconocene ketimides [Cp2Zr(Cl)NC(But)Ph] (7), and [Cp2Zr(Cl)NC(NMe2)2] (9), have been prepared by the transmetallation reactions between the appropriate lithiated organonitrogen compounds and zirconocene dichloride (2). In addition, their methylated derivatives [Cp2Zr(Me)N(CH2Ph)2] (6), [Cp2Zr(Me)NC(But)Ph] (8), and [Cp2Zr(Me)NC(NMe2)2] (10)

  锆茂[Cp 2 Zr（Cl）N（CH 2 Ph）2 ]（5）和锆茂酮[Cp 2 Zr（Cl）NC（Bu t）Ph]（7）和[Cp 2 Zr（Cl）N = C（NMe 2）2 ]（9）是通过适当的锂化有机氮化合物与二茂锆（2）之间的金属转移反应制备的。此外，它们的甲基化衍生物[Cp 2 Zr（Me）N（CH 2 Ph）2 ]（6），[Cp 2 Zr（Me）NC（Bu t）Ph]（8），和混合[Cp 2 Zr的（Me）的NC（NME 2）2 ]（10），制备了由每个复合物的反应5，7和9与的MeLi。化合物5和7的特征在于X射线晶体学和共晶配合物的结构[Cp 2 Zr（Cl）NC（Bu t）Ph] 0.4 [Cp 2 Zr（Me）NC（Bu t）相似地确定了Ph] 0.6（14）。所有物的5 - 10是在MAO助催化剂存在下乙烯聚合的活性催化剂。相反，没有使用B（C 6 F 5）3作
• Promoting oxo functionalization in the uranyl ion by ligation to ketimides
  作者：Lani A. Seaman、Elizabeth A. Pedrick、Guang Wu、Trevor W. Hayton

  DOI：10.1016/j.jorganchem.2017.08.007

  日期：2018.2

  Reaction of [UO2Cl2(THF)2]2 with 8 equiv of Li(N=CtBuPh) or 6 equiv of Li(N=CtBu2) affords the uranyl ketimide complexes, [Li(THF)(Et2O)]2[UO2(N=CtBuPh)4] (1) and [Li(THF)(TMEDA)][UO2(N=CtBu2)3] (2), respectively. Complexes 1 and 2 have been fully characterized, including analysis by X-ray crystallography. Most importantly, both complexes feature dative interactions between their lithium counterions and the

  [UO 2 Cl 2（THF）2 ] 2与8当量的Li（N = C t BuPh）或6当量的Li（N = C t Bu 2）反应，得到铀酰酮亚胺络合物[Li（THF）（ Et 2 O）] 2 [UO 2（N = C t BuPh）4 ]（1）和[Li（THF）（TMEDA）] [UO 2（N = C t Bu 2）3 ]（2）。配合物1和2已经被充分表征，包括通过X射线晶体学分析。最重要的是，这两种配合物的特征均在于它们的锂抗衡离子与铀酰氧代配体之间存在定性相互作用。这些相互作用可能是由于它们的UO键较弱所致，这是由于强供电子酮亚胺配体的阴离子N供体原子与铀酰片段的氧代配体之间的静电排斥引起的。
• Armstrong, David R.; Barr, Donald; Snaith, Ronald, Journal of the Chemical Society, Dalton Transactions, 1987, p. 1071 - 1082
  作者：Armstrong, David R.、Barr, Donald、Snaith, Ronald、Clegg, William、Mulvey, Robert E.、et al.

  DOI：——

  日期：——
• Synthesis of (1-Adamantylimido)vanadium(V) Complexes Containing Aryloxo, Ketimide Ligands: Effect of Ligand Substituents in Olefin Insertion/Metathesis Polymerization
  作者：Wenjuan Zhang、Kotohiro Nomura

  DOI：10.1021/ic800347n

  日期：2008.7.1

  A series of (1-adamantylimido)vanadium(V) complexes containing anionic donor ligands of the type, V(NAd)Cl-2(L) [Ad = 1-adamantyl; L = 0-2,6-Me2C6H3 (2), O-2,6-(Pr2C6H3)-Pr-i (3), N=(CBu2)-Bu-t (5), N=C(Bu-t)CH2SiMe3 (6), N=C(Bu-t)Ph (7), N=CPh2 (8)], have been prepared from V(NAd)Cl-3, which was in turn prepared from VOCl3 by treatment with 1-adamantylisocyanate in octane, by treatment with the corresponding lithium salts (lithium phenoxides, lithium ketimides) in Et2O. These complexes (2, 3, 5-8) were identified by NMR spectroscopy and elemental analysis, and the structures for 2 and 5 were determined by X-ray crystallography. The reaction of V(NAd)Cl-3 with 2,6-dimethylphenol in n-hexane afforded the tris(aryloxo) analogue V(NAd)(O-2,6-Me2C6H3)(3) (4), the structure of which was determined by X-ray crystallography. 8 gradually decomposed in toluene to give a dimeric species, [N(Ad)H-3](+)[V-2(mu(2)-Cl)(3)Cl-2(NAd)(2)(N=CPh2)(2)](-) (10), but 8 was stabilized as a PMe3 coordinated species, V(NAd)Cl-2-(N=Cph(2))(PMe3)(2) (9): the structures for 9 and 10 were determined by X-ray crystallography. These complexes were evaluated as catalyst precursors for ethylene polymerization in the presence of MAO. The ketimide analogues, especially 5, exhibited moderate catalytic activity, and the activity with a series of V(NAd)Cl-2(L)-MAO catalyst systems increased in the order: L = N=(CBu2)-Bu-t (5, 516 kg-PE/mol (.) V (.) h) > N=C(Bu-t)Ph (7, 300) > N=CPh2 (8, 105) > N=C(Bu-t)CH2SiMe3 (6, 70.8). These complexes (2, 3, 5, 6) were found to be effective as catalyst precursors for the ring-opening metathesis polymerization (ROMP) of norbomene (NBE) in the presence of MeMgBr and PMe3.
• Probing the 5f Orbital Contribution to the Bonding in a U(V) Ketimide Complex
  作者：Lani A. Seaman、Guang Wu、Norman Edelstein、Wayne W. Lukens、Nicola Magnani、Trevor W. Hayton

  DOI：10.1021/ja211875s

  日期：2012.3.14

  Reaction of UCl4 with 5 equiv of Li(N=(CBuPh)-Bu-t) generates the homoleptic U(IV) ketimide complex [Li(THF)(2)][U(N=(CBuPh)-Bu-t)(5)] (1) in 71% yield. Similarly, reaction of UCI4 with 5 equiv of Li(N=(CBu2)-Bu-t) affords [Li(THF)][U(N=(CBu2)-Bu-t)(5)] (2) in 67% yield. Oxidation of 2 with 0.5 equiv of I-2 results in the formation of the neutral U(V) complex U(N=(CBu2)-Bu-t)(5) (3). In contrast, oxidation of 1 with 0.5 equiv of I-2, followed by addition of 1 equiv of Li(N=(CBuPh)-Bu-t), generates the octahedral U(V) ketimide complex [Li][U(N=(CBuPh)-Bu-t)(6)] (4) in 68% yield. Complex 4 can be further oxidized to the U(VI) ketimide complex U(N=(CBuPh)-Bu-t)(6) (5). Complexes 1-5 were characterized by X-ray crystallography, while SQUID magnetometry, EPR spectroscopy, and UV-vis-NIR spectroscopy measurements were also preformed on complex 4. Using this data, the crystal field splitting parameters of the f orbitals were determined, allowing us to estimate the amount of f orbital participation in the bonding of 4.