Zirconium Complexes Containing Tetradentate O,P,P,O Ligands: Ethylene and Propylene Polymerization Studies

Abstract

The synthesis of a series of zirconium complexes bearing a linear diphosphanyl-bisphenoxide O,P,P,O ligand is described. The diphosphanyl- bisphenol proligand was prepared from Ph(Cl)PC2H4P(Cl)Ph as a 1:1 mixture of rac and meso diastereomers, which could be separated as a result of their differing solubilities in methanol. A relatively low barrier to phosphine inversion (ΔG†373K = 28.02(3) kcal/mol) allows interconversion of the two isomers. The zirconium dichloride complex of each diastereomer was prepared via treatment of ZrCl 4(THF)2 with the sodium (rac) or lithium (meso) salt of the respective bisphenol. Crystallographic and NMR analyses revealed a cis-α structure for the complex beari..