American Chemical Society
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Impact of Preferential π‑Binding in Catalyst-Transfer Polycondensation of Thiazole Derivatives

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journal contribution
posted on 2016-12-09, 18:49 authored by Mitchell L. Smith, Amanda K. Leone, Paul M. Zimmerman, Anne J. McNeil
Polymerizing electron-deficient arenes in a controlled, chain-growth fashion remains a significant challenge despite a decade of research on catalyst-transfer polycondensation. The prevailing hypothesis is that the chain-growth mechanism stalls at a strongly associated metal–polymer π-complex, preventing catalyst turnover. To evaluate this hypothesis, we performed mechanistic studies using thiazole derivatives and identified approaches to improve their chain-growth polymerization. These studies revealed a surprisingly high barrier for chain-walking toward the reactive C–X bond. In addition, a competitive pathway involving chain-transfer to monomer was identified. This pathway is facilitated by ancillary ligand dissociation and N-coordination to the incoming monomer. We found that this chain-transfer pathway can be attenuated by using a rigid ancillary ligand, leading to an improved polymerization. Combined, these studies provide mechanistic insight into the challenges associated with electron-deficient monomers as well as ways to improve their living, chain-growth polymerization. Our mechanistic studies also revealed an unexpected radical anion-mediated oligomerization in the absence of catalyst, as well as a surprising oxidative addition into the thiazole C–S bond in a model system.