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• W4313252304 endingPage "10830" @default.
• W4313252304 startingPage "10821" @default.
• W4313252304 abstract "Catalyst-transfer polymerization (CTP) is a chain-growth method used to synthesize conjugated polymers. Although CTP works well for most donor-type monomers, the polymerization stalls with thieno[3,2-b]thiophene when using Ni catalysts. Previous reports have rationalized this result by suggesting that the catalyst is trapped in a Ni0 π-complex with the highly electron-rich arene. In this study, evidence is provided that the catalyst trap is more likely a NiII complex that arises from oxidative insertion of Ni0 into the C–S bonds of thieno[3,2-b]thiophene. This result is consistent with the known reactivity of Ni0 complexes toward S-heteroarenes and is supported herein by 31P nuclear magnetic resonance spectra acquired in situ, as well as data collected from small-molecule model reactions and density-functional theory simulations of the polymerization. We propose that this C–S insertion pathway and related off-cycle reactions may be relevant to understanding or enabling the CTP of other monomers with fused thiophenes." @default.
• W4313252304 created "2023-01-06" @default.
• W4313252304 creator A5001605031 @default.
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• W4313252304 date "2022-12-07" @default.
• W4313252304 modified "2023-09-27" @default.
• W4313252304 title "Rethinking Catalyst Trapping in Ni-Catalyzed Thieno[3,2-<i>b</i>]thiophene Polymerization" @default.
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• W4313252304 doi "https://doi.org/10.1021/acs.macromol.2c01521" @default.
• W4313252304 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/37396500" @default.
• W4313252304 hasPublicationYear "2022" @default.
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