title: Cleavage and reorganization of Zr-C/Si-C bonds leading to Zr/Si-N organometallic and heterocyclic compounds.
abstract: The t-BuCN-stabilized zirconacyclopropene-azasilacyclopentadiene complexes 2 are generated in situ in high yields from the Si-tethered diynes, Cp(2)Zr(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 (S(8)), 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.
authors.affiliation: Beijing National Laboratory of Molecular Sciences, College of Chemistry, Peking University, Beijing 100871, China.
authors.forename: Shaoguang
authors.initials: S
authors.lastname: Zhang
authors.forename: Wen-Xiong
authors.initials: WX
authors.lastname: Zhang
authors.forename: Jing
authors.initials: J
authors.lastname: Zhao
authors.forename: Zhenfeng
authors.initials: Z
authors.lastname: Xi