Tailored Strength Neighboring Group Interactions Switch Polymerization to Dimerization Catalysis

A combined experimental and theoretical study elucidates how Ni center dot center dot center dot O neighboring group interactions drastically switch catalytic properties toward ethylene. A range of salicylaldiminato complexes with aryloxy groups in the 2,6-position of the N-phenyl group was found to dimerize and oligomerize ethylene to butenes and branched oligomers (C-4, C-6, C-8, C-10, ...) in pressure reactor experiments, while corresponding reference catalysts with arylmethylene groups yield linear polyethylene with M-n of 100.000 g mol(-1) While both types of catalysts consume ethylene with similar high activities (10(5) turnovers h(-1)), the rate of ss-hydride elimination (BHE) is much increased for the case of aryloxy substitution. Density functional theory (DFT) studies show that formation of the relevant cis agostic complex from which BHE occurs by displacement of ethylene from the cis-alkyl olefin complex is promoted by an Ni center dot center dot center dot O interaction. This low energy pathway renders chain transfer competitive with insertion chain growth. The resulting Ni center dot center dot center dot O intermediate is rather stable and similar in energy to key species of catalysis (ss-agostic and alkyl olefin complexes) but barely not yet an energetic sink that would impede catalysis.