Systematic Catalyst Variation for Improved Stereoselective Epoxide Polymerization: Subtle Modifications Resulting in...

Isotactic poly(propylene oxide) (iPPO) is a semicrystalline polyether that has emerged as a high-strength, photodegradable material for marine applications. To improve the accessibility of iPPO, catalysts with higher activity and selectivity are required. Using rational catalyst design informed by computational insights, we developed a flexibly tethered, bimetallic chromium catalyst exhibiting high enantioselectivity (k_rel ∼ 100) and unprecedented activity (TOF ∼ 50,000 h^-1) for propylene oxide (PO) polymerization. Mechanistic studies reveal that high enantioselectivity originates from increased steric bulk at the ortho position of the salicylimine moiety, which increases steric repulsion between the alkoxide chain end and the ligand in the disfavored transition state. Furthermore, introducing geminal dimethyl groups that rigidify the flexible tether between the two ligand moieties significantly enhances catalyst activity by destabilizing the resting state during polymerization. The catalyst remains active at loadings as low as 0.5 ppm, enabling the synthesis of colorless, tough iPPO.