The development of practical routes to functional polyolefins (f-PO) directly from simple alkenes with tunable microstructure and sequence control is a long-standing challenge. This presentation will discuss complementary strategies we have pursued to access different f-PO architectures. A series of P(V)-P(III) ligands have been discovered that generate nickel(II) catalysts capable of producing linear, statistical f-PO copolymers with molecular weights and sequences that mimic linear low-density polyethylene. Mechanistic data have established how these catalysts differ from existing systems by accessing unusual “electron-rich metal cation” behavior that tempers Lewis acidity, needed for functional group compatibility, while maintaining electrophilic character for high intrinsic reactivity. Alternatively, functional groups can be positioned exclusively at chain ends to access telechelic f-PO using bidirectional catalysts that are rapidly assembled from abundant starting materials.

Complementary functional polyolefin architectures by uni- and bidirectional insertion polymerization

ACS Spring Meeting 2021

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