Synthesis and structural studies of nonsymmetric guanidinato zirconium and hafnium complexes and catalytic behavior for ethylene polymerization

INOR 286

Meisu Zhou, meisuzhou@yahoo.com.cn1, Hongbo Tong, tong@sxu.edu.cn1, Wenhua Sun, whsun@iccsa.ac.cn2, and Diansheng Liu, dsliu@sxu.edu.cn1. (1) Institute of Applied Chemistry, Shanxi University, No. 92 Wucheng Road, Taiyuan, 030006, China, (2) State Key Laboratory for Engineering Plastics and Center of Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100080, China
The guanidinato complexes have been extensively investigated in coordination chemistry. Beyond the fundamental investigation of guanidinate complexes related to their structural features, some guanidinato complexes have been identified as initiators or catalysts for polymerization reactions. Here we report equivalent addition reactions of PhN(SiMe3) anion to nitriles, RCN (R = dimethylamido, 1-peperidino), which result in the formation of the 1:1 adducts [(Et2O)LiN(SiMe3)C(NMe2)N(Ph)]2, [(THF)LiN(SiMe3)C(NMe2)N(Ph)]2 and [(Et2O)LiN(SiMe3)C(N(CH2)5)N(Ph)]2 , which further reacted with zirconium or hafnium tetrachloride to form a series of guanidinato complexes of Zr and Hf exhibiting the general formulas [PhNC(R)NSiMe3]3MCl (R = dimethylamido, 1-peperidino; M = Zr, Hf). The metal complexes were well characterized by NMR and microanalysis, moreover, their unambiguous molecular structures were finally confirmed by single crystal X-ray diffraction analysis. In addition, the complexes were found to be active for ethylene polymerization.
 

Organometallic Catalysts
7:00 PM-10:00 PM, Sunday, August 19, 2007 BCEC -- Exhibit Hall - B2, Poster

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007