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Three well\u2010known NHCs; SIPr (\n 1a<\/jats:bold>\n ), IPr (\n 1b<\/jats:bold>\n ), and Me\u2010IPr (\n 1c<\/jats:bold>\n ) (SIPr\u00a0=\u00a0C{N(Dipp)CH\n 2<\/jats:sub>\n }\n 2<\/jats:sub>\n , IPr\u00a0=\u00a0C{N(Dipp)CH}\n 2<\/jats:sub>\n ; Me\u2010IPr\u00a0=\u00a0C{N(Dipp)CCH\n 3<\/jats:sub>\n }\n 2<\/jats:sub>\n ; Dipp\u00a0=\u00a02,6\u2010\n i<\/jats:italic>\n Pr\n 2<\/jats:sub>\n C\n 6<\/jats:sub>\n H\n 3<\/jats:sub>\n ); were functionalized at the C2 position using 4\u2010bromo\u2010\n p<\/jats:italic>\n \u2010terphenyl (\n p<\/jats:italic>\n \u2010TerBr) and 5\u2032\u2010bromo\u2010\n m<\/jats:italic>\n \u2010terphenyl (\n m<\/jats:italic>\n \u2010TerBr) under nickel catalysis, yielding the corresponding cations [(NHC)\n p<\/jats:italic>\n \u2010Ter]Br (\n 2a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n ) and [(NHC)\n m<\/jats:italic>\n \u2010Ter]Br (\n 3a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n ), respectively. Cyclic voltammetry (CV) measurements of\n 2a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n reveal two distinct reversible redox events, while\n 3a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n exhibit one reversible and one irreversible or quasi\u2010reversible wave. Reduction of\n 2a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n and\n 3a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n with KC\n 8<\/jats:sub>\n readily affords stable radicals [(NHC)\n p<\/jats:italic>\n \u2010Ter]\n \u25cf<\/jats:sup>\n (\n 4a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n ) and [(NHC\u2010\n m<\/jats:italic>\n \u2010Ter]\n \u25cf<\/jats:sup>\n (\n 5a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n ), isolated as crystalline solids. Further reduction of\n 4a<\/jats:bold>\n \u2013\n c<\/jats:bold>\n produces diamagnetic anions [(NHC)\n p<\/jats:italic>\n \u2010Ter]K (\n 6a<\/jats:bold>\n \u2013\n c\u2010K<\/jats:bold>\n ), consistent with the electrochemical data. In contrast,\n 5b<\/jats:bold>\n and\n 5c<\/jats:bold>\n are unreactive toward KC\n 8<\/jats:sub>\n under similar conditions, while\n 5a<\/jats:bold>\n (derived from the more electrophilic NHC\n 1a<\/jats:bold>\n ) can be reduced to the corresponding anion [(SIPr)\n m<\/jats:italic>\n \u2010Ter]K (\n 7a\u2010K<\/jats:bold>\n ). Selected compounds have been characterized by spectroscopic techniques and single\u2010crystal X\u2010ray diffraction, with computational studies supporting the experimental findings. The results highlight how the NHC and the C2\u2010terphenyl substituent influence the properties and stability of the resulting species.\n <\/jats:p>","DOI":"10.1002\/anie.202520260","type":"journal-article","created":{"date-parts":[[2025,10,22]],"date-time":"2025-10-22T12:37:01Z","timestamp":1761136621000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["NHC\u2010Terphenyl Radicals and Anions: Tuning Stability and Redox Properties via Substituent Patterning"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5187-2242","authenticated-orcid":false,"given":"Henric","family":"Steffenfauseweh","sequence":"first","affiliation":[{"name":"Molecular Inorganic Chemistry and Catalysis Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universit\u00e4t Bielefeld Universit\u00e4tsstrasse 25 D\u201033615 Bielefeld 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Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universit\u00e4t Bielefeld Universit\u00e4tsstrasse 25 D\u201033615 Bielefeld Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bas","family":"de Bruin","sequence":"additional","affiliation":[{"name":"University of Amsterdam (UvA) Faculty of Science Van 't Hoff Institute for Molecular Sciences (HIMS) Homogeneous and Supramolecular Catalysis Group Science Park 904 Amsterdam 1098 XH The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2146-5432","authenticated-orcid":false,"given":"Rajendra S.","family":"Ghadwal","sequence":"additional","affiliation":[{"name":"Molecular Inorganic Chemistry and Catalysis Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universit\u00e4t Bielefeld Universit\u00e4tsstrasse 25 D\u201033615 Bielefeld 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