A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R3Si+ Species

The silylium-like surface species [(Pr3Si)-Pr-i]-[(O-F)(3)Al-OSi )] activates (N boolean AND N)Pd(CH3)Cl (N boolean AND N= Ar-N=CMeMeC=N-Ar, Ar = 2,6-bis(diphenylmethyl)-4-methylbenzene) by chloride ion abstraction to form [(N boolean AND N)Pd-CH3][((RO)-O-F)(3)Al-OSi )] (1). A combination of FTIR, solid-state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N boolean AND N)Pd(CH3)Cl activated with Na[B(Ar-F)(4)]. Multinuclear C-13{Al-27} RESPDOR and H-1-{F-19} S-REDOR experiments are consistent with a weakly coordinated ion-pair between (N boolean AND N)Pd-CH3+ and [((RO)-O-F)(3)Al-OSi )]. 1 catalyzes the polymerization of ethylene with similar activities as [(N boolean AND N)Pd-CH3](+) in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.