Cleavage and Reorganization of Zr−C/Si−C Bonds Leading to Zr/Si−N Organometallic and Heterocyclic Compounds

The t-BuCN-stabilized zirconacyclopropene−azasilacyclopentadiene complexes 2 are generated in situ in high yields from the Si-tethered diynes, Cp2Zr(II) species, and 2 equiv of t-BuCN via a coordination-induced Zr−C/Si−C bond cleavage and reorganization. Complexes 2 have been demonstrated to be synthetically very useful. A variety of novel Zr/Si organo-bimetallic compounds and Si/N heterocyclic compounds, such as azasilacyclopentadienes, azasilacyclohexadienes, and allenylazazirconacycles, are obtained in high yields when complexes 2 are treated with ketones, carbodiimides, alkynes, elemental sulfur (S8), acid chlorides, or nitriles. In this chemistry, t-BuCN behaves as both an initiator and a brake/release handle to initiate and control the reaction process.