Allosteric Effects in Ethylene Polymerization Catalysis. Enhancement of Performance of Phosphine-Phosphinate and Phosphine-Phosphonate Palladium Alkyl Catalysts by Remote Binding of B(C6F5)

Remote binding of B(C6F5)(3) to (PPO)PdMeL (L = pyridine or lutidine) or {(PPO)PdMe}(2) ethylene polymerization catalysts that contain phosphine-arenephosphinate or phosphine-arenephosphonate ligands (PPO- = [1-PAr2-2-PR ' O-2-Ph](-): Ar = R ' = Ph (1a); Ar = Ph, R ' = OEt (1b); Ar = Ph, R ' = (OPr)-Pr-i (1c); Ar = 2-OMe-Ph, R ' = (OPr)-Pr-i (1d)) significantly increases the catalyst activity and the molecular weight of the polyethylene (PE) product. In the most favorable case, in situ conversion of (1d)PdMe(py) to the base-free adduct {1d-B(C6F5)(3)}PdMe increases the ethylene polymerization activity from 9.8 to 5700 kg mol(-1) h(-1) and the M-n of the PE product from 9030 to 99200 Da (80 degrees C, 410 psi). X-ray structural data, trends in ligand lability, and comparative studies of BF3 activation suggest that these allosteric effects are primarily electronic in origin. The B(C6F5)(3) binding enhances the chain growth rate (R-growth) by increasing the degree of positive charge on the Pd center. This effect does not result in the large increase in the chain transfer rate (R-transfer) and concomitant reduction in PE molecular weight seen in previous studies of analogous (PO)PdRL catalysts that contain phosphine-arenesulfonate ligands, because of the operation of a dissociative chain transfer process, which is inhibited by the increased charge at Pd.