tetrachloro(N,N'-bis(3,5-dimethylphenylimino)acenaphthylene)titanium(IV) | 1213265-99-6

• 英文名称: tetrachloro(N,N'-bis(3,5-dimethylphenylimino)acenaphthylene)titanium(IV)
• CAS: 1213265-99-6
• 化学式: C₂₈H₂₄Cl₄N₂Ti
• 分子量: 578.204
• InChiKey: QQCNTWJWBHJKSI-TVYDCKAQSA-J

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：

  吡啶 、 tetrachloro(N,N'-bis(3,5-dimethylphenylimino)acenaphthylene)titanium(IV) 以 二氯甲烷 为溶剂， 以0%的产率得到TiCl₄(Py)₂
  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
• 作为产物：
  描述：

  TiCl₄(Py)₂ 、 α-diimine N,N′-bis(3,5-dimethylphenylimino)acenaphthenequinonate 以 二氯甲烷 为溶剂， 生成 tetrachloro(N,N'-bis(3,5-dimethylphenylimino)acenaphthylene)titanium(IV)
  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