A Binary Silicon-Centered Organoboron Catalyst with Superior Performance to That of Its Bifunctional Analogue

This work reported that a silicon-centered alkyl borane/ammonium salt binary (two-component) catalyst exhibits much higher activity than its bifunctional analogue (one-component) for the ring-opening polymerization of propylene oxide, showing 7.3 times the activity of its bifunctional analogue at a low catalyst loading of 0.01 mol %, and even 15.3 times the activity at an extremely low loading of 0.002 mol %. By using 19F NMR spectroscopy, control experiments, and theoretical calculation we discovered that the central silicon atom displays appropriate electron density and a larger intramolecular cavity, which is useful to co-activate the monomer and to deliver propagating chains, thus leading to a better intramolecular synergic effect than its bifunctional analogue. A unique two-pathway initiation mode was proposed to explain the unusual high activity of the binary catalytic system. This study breaks the traditional impression of the binary Lewis acid/nucleophilic catalyst with poor activity because of the increase in entropy. In general, two-component catalysts containing Lewis pairs are inferior to one-component ones due to the lack of intramolecular synergy. A silicon-centered bimolecular catalyst has been developed that exhibits a rare higher activity than its unimolecular analogue, even at low loadings. A unique two-path initiation mode was proposed to explain its exceptional catalytic performance in the ring-opening polymerization of propylene oxide.image