{"doi":"10.1021/acs.macromol.2c01521","title":"Rethinking Catalyst Trapping in Ni-Catalyzed Thieno[3,2-<i>b</i>]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 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.","journal":"Macromolecules","year":2022,"id":281873,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":8,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9498,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2022-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":957523,"name":"Jessica L. Tami","orcid":"0000-0003-3106-5790","position":1,"is_corresponding":false},{"id":343751,"name":"Paul M. Zimmerman","orcid":"0000-0002-7444-1314","position":2,"is_corresponding":false},{"id":957524,"name":"Anne J. McNeil","orcid":"0000-0003-4591-3308","position":3,"is_corresponding":false},{"id":957522,"name":"Matthew D. Hannigan","orcid":"0000-0002-2267-1388","position":0,"is_corresponding":true}],"reference_count":57,"raw_metadata":null,"created_at":"2026-07-19T00:29:15.734856Z","pmid":"37396500","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}