An Approach to Catalyst Design: Cyclopentadienyl-Titanium Phosphinimide Complexes in Ethylene Polymerization
作者:Douglas W. Stephan、Jeffrey C. Stewart、Frédéric Guérin、Silke Courtenay、James Kickham、Emily Hollink、Chad Beddie、Aaron Hoskin、Todd Graham、Pingrong Wei、Rupert E. v. H. Spence、Wei Xu、Linda Koch、Xiaoliang Gao、Daryll G. Harrison
DOI:10.1021/om020954t
日期:2003.4.1
for polymerization catalyst design has been developed based on the steric and electronic analogy of bulky phosphinimides to cyclopentadienyl ligands. To this end, the family of complexes of the form (Cp†)TiCl2(NPR3) has been prepared and characterized. Alkyl and aryl derivatives of these species have also been synthesized, and a number have been evaluated for use as catalyst precursors in olefin polymerization
The iminophosphoranyldichlorophosphines Ph3PNPCl2 (2a), pTol3PNPCl2 (2b), and Cy3PNPCl2 (2c) were synthesized by reaction of trimethylsilyliminophosphoranes R3PNSiMe3 (R = Ph, pTol, Cy) with an equimolar amount of PCl3. The compounds 2b and 2c were isolated in pure form for the first time and characterized by 31P, 1H and 13C NMR spectroscopy. The molecular structures of the iminophosphoranyl dichlorophosphines