1,2,3,4,5-pentamethylcyclopenta-1,3-diene;titanium(4+);1-N,2-N,4-N-tricyclohexyl-3-methylidenebutane-1,2,4-triimine | 334976-94-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1,2,3,4,5-pentamethylcyclopenta-1,3-diene;titanium(4+);1-N,2-N,4-N-tricyclohexyl-3-methylidenebutane-1,2,4-triimine
• CAS: 334976-94-2
• 化学式: C₄₃H₆₅N₃Ti
• 分子量: 671.889
• InChiKey: PJQYXSFBWVJHRQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.77
• 重原子数：
  47
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  37.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  异氰环已烷 、 (C5(CH3)5)Ti(vinylidene) 以 not given 为溶剂， 生成 1,2,3,4,5-pentamethylcyclopenta-1,3-diene;titanium(4+);1-N,2-N,4-N-tricyclohexyl-3-methylidenebutane-1,2,4-triimine
  参考文献：
  名称：

  Beckhaus, Ruediger, Angewandte Chemie - International Edition, 1997, vol. 36, p. 687 - 713

  摘要：

  DOI：

文献信息

• Reactions of the Titanaallene Intermediate [Cp*₂TiCCH₂] with Isonitriles:  An Approach to the Chemistry of Radialene Type Molecules
  作者：Cristina Santamaría、Rüdiger Beckhaus、Detlev Haase、Rainer Koch、Wolfgang Saak、Isabelle Strauss

  DOI：10.1021/om000929s

  日期：2001.4.1

  The titanaallene intermediate [Cp*Ti-2=C=CH2] (2), obtained via methane elimination from Cp*Ti-2(CH=CH2)Me (1), reacts with an excess of cyclohexylisonitrile (CyNC), to give the five-membered metallacycle Cp*2TiC(=NCy)C(=NCy)C(=CH2)C=NCy (4), which exhibits a radialene substructure. This reaction occurs by a [2+1] addition followed by subsequent insertion of two molecules of isonitrile. A [2+1] addition product is isolated from the reaction of 1 with 2,6-dimethylphenylisonitrile (ArNC) in 1:2 ratio in the form of the azabutatriene complex (Cp*Ti-2(CNAr)(eta (2)-H2CC=C=NAr) (5). The X-ray structure analysis of 5 reveals a pentacoordinated geometry consisting of a eta (2)-C,C-azabutatriene moiety stabilized by a further ArNC ligand. Whereas 5 is stable in the solid state (dec 102-105 degreesC), in solution (20 degreesC) one molecule of isonitrile is released. Subsequent intramolecular C-H bond activation and C-C bond formation afford product 7. The latter can be directly isolated from reaction of 2 with 1 equiv of ArNC. The treatment of the titanaallene species 2 with 3 equiv of ArNC leads, through the insertion of two isonitrile molecules into the Ti-CH2 bond in complex 5, to the five-membered ring complex 8, Cp*2TiC(=NAr)C(=NAr)CH2C=C=NAr. The molecular structure of 8; shows a planar titanacyclopentane. Density functional theory calculations confirm the terminal C,C-coordination mode as found in 5 as the preferred arrangement against the C,N- or internal C,C-coordination modes.