(N,N'-bis(2,6-diisopropylphenylimino)acenaphthylene)TiCl4 | 1213265-97-4

• 英文名称: (N,N'-bis(2,6-diisopropylphenylimino)acenaphthylene)TiCl4
• 英文别名: tetrachloro(N,N'-bis(2,6-diisopropylphenylimino)acenaphthylene)titanium(IV)；(N,N'-bis(2,6-diisopropylphenylimino)acenaphthylene)TiCl₄；(dpp-BIAN)TiCl₄
• CAS: 1213265-97-4
• 化学式: C₃₆H₄₀Cl₄N₂Ti
• 分子量: 690.419
• InChiKey: INGFOTQIKYZRNI-DDUJJQHXSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (N,N'-bis(2,6-diisopropylphenylimino)acenaphthylene)TiCl4 、 (2,2-二甲基丙基)锂 以 正戊烷 为溶剂， 反应 1.0h， 以85%的产率得到[(N,N'-bis(2,6-diisopropylphenylamido)acenaphthylene)Ti(neopentyl)₂]
  参考文献：
  名称：

  还原性氧化还原活性配体支持的低配位钛合成子的合成与反应性

  摘要：

  为了进一步探索双芳基ino并配体在早期过渡金属络合物中的反应性和氧化还原能力，配位不饱和钛合成子[（dpp-BAAN）Ti（R）2 ]（[dpp-BAAN] 2– = N，N- ' -双（2,6-二diisopropylphenylamido）苊烯和R = O吨卜（2）或CH 2 C（CH 3）3（3）），其中配位体是由两个电子还原的BAAN，分别为通过空间诱导的自由基消除反应以高收率分离得到。的另外p -甲苯基叠氮化物复合物3开始还原性消除新戊基配体以产生推定的亚氨基。通过氯化物配体的第二次氧化加成来捕获亚胺类，以产生钛亚胺络合物[[dpp-BIAN] Ti [= N（4-C 6 H 4 Me）] Cl 2（4）。这些反应表明，BAAN配体可提供氧化还原当量以增强反应性，包括在d 0金属中心的氧化加成和还原消除。

  DOI：

  10.1021/acs.inorgchem.6b00404
• 作为产物：
  描述：

  四氯化钛 、 1,2-双-[(2,6-二异丙基苯基)亚氨基]苊 以 二氯甲烷 为溶剂， 以90%的产率得到(N,N'-bis(2,6-diisopropylphenylimino)acenaphthylene)TiCl4
  参考文献：
  名称：

  Steric Control of Coordination Geometry in Titanium-Imido Complexes of N,N′-bis(arylimino)acenaphthylene Ligands

  摘要：

  Titanium complexes of N,N'-bis(arylimino)acenaphthylene (BIAN) alpha-diimine ligands with varied steric profiles have been prepared. Coordination of the BIAN ligand derivatives to TiCl4 afforded the adducts (dpp-BIAN)TiCl4 (1a), (tmp-BIAN)-TiCl4 (1b), and (dmp-BIAN) TiCl4 (1c) (dpp = 2,6-diisopropylphenyl; tmp = 2,4,6-trimethylphenyl; dmp = 3,5-dimethylphenyl). While the least sterically crowded complex 1c is robust toward loss of the diimine ligand, the dpp-BIAN and tmp-BIAN ligands are readily displaced by pyridine from the more crowded derivatives 1a and 1b, respectively. The crowded profiles engendered by the tmp-BIAN and dpp-BIAN ligands result in the formation of five-coordinate titanium-imide complexes, (dpp-BIAN)TiCl2(=(NBu)-Bu-t) (2a) and (tmp-BIAN)TiCl2(=(NBu)-Bu-t) (2b), upon addition of (BuNH2)-Bu-t to solutions of 1a or 1b, respectively. Single-crystal X-ray diffraction studies reveal a square pyramidal coordination environment with an apical imide ligand and a short Ti-N distance, consistent with a Ti-N triple bond. Conversely, the less crowded dmp-BIAN ligand affords a six-coordinate titanium imido complex, (dmp-BIAN)TiCl2(=(NBu)-Bu-t)((NH2Bu)-Bu-t) (4), upon treatment of 1c with (BuNH2)-Bu-t. Surprisingly the imido ligand is coordinated trans to one arm of the diimine. This six coordinate species is fluxional in solution, and exchange and variable temperature H-1 NMR experiments suggest dissociation of the coordinated (BuNH2)-Bu-t ligand to generate a five-coordinate imido intermediate analogous to 2a and 2b.

  DOI：

  10.1021/ic902101z