Iron-based catalysts are described that rely on ligand hemilability as a key mechanistic feature to control reactivity and selectivity in polymerization reactions. Bis(imino)pyridine iron siloxide complexes are described that effect the stereoselective ring opening polymerization of lactide by a stereocontrol mechanism that relies on the dissociation of an imine arm of the bis(imino)pyridine ligand. Similarly, MAO activation of an iron-based complexes supported by alkylated bis(pyridylimino)isoindolate ligands are shown to be active catalysts for the polymerization of ethylene through a mechanism that is regulated by dissociation of the pyridine arm of the ligand. The mechanisms used by both catalysts were deduced based on experimental data and are unique compared to most catalysts used for each reaction. These observations open new avenues for catalyst design that are made possible by the dynamic behavior of the supporting ligand.<br/>

Polymerization catalysts that benefit from dynamic ligand behavior

253rd National Meeting (2017)

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