Formation of Zirconocenes Containing Vinyl-imine and Keteniminate Species from Zirconacycles and Diphenylacetonitrile

The first well-defined zirconocene complexes processing vinyl-imine and keteniminate species have been achieved from zirconacyclopentenes or zirconacyclopentadienes and 2 equiv of Ph2CHCN. Multifunctional effect of Ph2CHCN is observed for the first time in one system. This process proceeds via the azazirconacyclopentadiene intermediate and its intramolecular proton transfer. Moreover, beta,beta'-C-C bond cleavage of tetra-alkyl-substituted zirconacyclopentadienes is observed for the first time under the appropriate conditions.