研究室工作进展 October 13, 2010
研究室工作进展 October 13, 2010
Cleavage and Reorganization of Zr-C/Si-C Bonds Leading to Zr/Si-N Organometallic and Heterocyclic Compounds
Shaoguang Zhang, Wen-Xiong Zhang, Jing Zhao, and Zhenfeng Xi*
J. Am. Chem. Soc. 2010, 132, 14042-14045.
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 equivalents of t-BuCN, via a coordination-induced Zr-C/Si-C bond cleavage and re-organization. Complexes 2 have been demonstrated to be synthetically very useful. A variety of novel Zr/Si organo-bi-metallic compounds and Si/N heterocyclic compounds, such as azasilacyclopentadienes, azasilacyclohexadienes and allenyl-aza-zirconacycles, are obtained in high yields when complexes 2 are treated with ketones, carbodiimides, alkynes, elemental sulfur (S8), acid chlorides, and nitriles, respectively. In this chemistry, t-BuCN behaves as both an initiator and a brake/release handle to initiate and control the reaction process.