| 334976-96-4

• CAS: 334976-96-4
• 化学式: C₃₁H₄₁NTi
• 分子量: 475.553
• InChiKey: RMILHJPEBSRFNU-LGKSSORPSA-N

反应信息

• 作为产物：
  描述：

  [(C5Me5)2Ti(2,6-dimethylphenylisonitrile)(η2-H2CC=C=NC6H3Me2-2,6)] 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Reactions of the Titanaallene Intermediate [Cp*₂TiCCH₂] with Isonitriles:  An Approach to the Chemistry of Radialene Type Molecules

  摘要：

  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.

  DOI：

  10.1021/om000929s