Rethinking Catalyst Trapping in Ni-Catalyzed Thieno[3,2-b]thiophene Polymerization.

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 Ni^II 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 spectr

SUBMITTER: Hannigan MD 

PROVIDER: S-EPMC10312364 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature