Formation of Hydroxyindenyl and Vinylidene Ligands by Reaction of Internal Alkynes with Cp*Fe(CO)(NCMe)Ph

The reactivity of Cp*Fe­(CO)­(NCMe)­Ph (1) (Cp* = pentamethyl­cyclopentadienyl) with internal alkynes has been studied. Reactions of 1 with dihydrocarbyl-substituted alkynes result in the formation of pentamethyl­cyclopentadienyl hydroxyindenyl sandwich complexes. A divergent reaction pathway is observed in the case of bis­(trimethylsilyl)­acetylene, where a neutral Fe vinylidene is isolated. The reactions of hydrocarbyl trimethylsilyl-substituted alkynes with complex 1 result in the formation of the pentamethyl­cyclopentadienyl hydroxyindenyl sandwich complexes. This reactivity suggests the necessity of two trimethylsilyl groups for vinylidene formation.

本研究针对配合物Cp*Fe(CO)(NCMe)Ph（1，其中Cp*为五甲基环戊二烯基(pentamethylcyclopentadienyl)）与内炔烃的反应活性展开了探究。配合物1与二烃基取代炔烃的反应可生成五甲基环戊二烯基羟基茚三明治配合物。在双(三甲基硅基)乙炔的反应体系中，观测到一条分支反应路径，成功分离得到中性铁亚乙烯基配合物。烃基三甲基硅基取代炔烃与配合物1的反应同样生成五甲基环戊二烯基羟基茚三明治配合物。上述反应活性表明，生成铁亚乙烯基产物需要两个三甲基硅基取代基。