Synthesis of Semicrystalline Polyolefin Materials: Precision Methyl Branching via Stereoretentive Chain Walking

We report the discovery of C2-symmetric nickel catalysts capable of the regio- and isoselective polymerization of 1-butene to produce isotactic 4,2-poly­(1-butene), a new semi-crystalline polyolefin. The catalyst exhibits enantioface selectivities as high as 84% and the resulting polymers display melting temperatures up to 86 °C. This system marks a rare example of preserving stereochemistry through a chain walking polymerization process.