{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Silva-Munoz M"],"funding":["Ministerio de Ciencia, Innovaci?n y Universidades"],"pagination":["25151-25160"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC12754753"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["64(51)"],"pubmed_abstract":["We report the synthesis and characterization of rhodium and iridium complexes featuring a naphthalene-diimide (NDI)-functionalized N-heterocyclic carbene (NHC) ligand, in which the NDI unit is directly attached through an imide nitrogen. Electrochemical and spectroelectrochemical studies reveal that one- and two-electron reductions of the NDI moiety moderately enhance the electron-donating ability of the ligand, albeit to a lesser extent than in analogues where the NDI is fused to the carbene backbone. Catalytic investigations demonstrate that the iridium complexes efficiently promote the <i>N</i>-methylation of anilines with methanol via a borrowing-hydrogen pathway, outperforming the rhodium analogue. One-electron reduction of the NDI-NHC ligand leads to reversible deactivation of the catalyst, providing direct evidence for redox-switchable control of catalytic activity. Kinetic analyses and substrate studies indicate that imine reduction, rather than methanol dehydrogenation, constitutes the rate-determining step. These findings highlight NDI-NHC ligands as versatile redox-responsive platforms for fine-tuning electronic properties and catalytic performance in hydrgen-borrowing transformations."],"journal":["Inorganic chemistry"],"pubmed_title":["Redox-Switchable Naphthalenediimide-NHC Iridium Complexes for Switchable Catalysis in Aniline Methylation with Methanol."],"pmcid":["PMC12754753"],"funding_grant_id":["PID2024-158991NB-I00","TED2021-130647B-I00"],"pubmed_authors":["Martinez-Agramunt V","Poyatos M","Silva-Munoz M","Peris E"],"additional_accession":[]},"is_claimable":false,"name":"Redox-Switchable Naphthalenediimide-NHC Iridium Complexes for Switchable Catalysis in Aniline Methylation with Methanol.","description":"We report the synthesis and characterization of rhodium and iridium complexes featuring a naphthalene-diimide (NDI)-functionalized N-heterocyclic carbene (NHC) ligand, in which the NDI unit is directly attached through an imide nitrogen. Electrochemical and spectroelectrochemical studies reveal that one- and two-electron reductions of the NDI moiety moderately enhance the electron-donating ability of the ligand, albeit to a lesser extent than in analogues where the NDI is fused to the carbene backbone. Catalytic investigations demonstrate that the iridium complexes efficiently promote the <i>N</i>-methylation of anilines with methanol via a borrowing-hydrogen pathway, outperforming the rhodium analogue. One-electron reduction of the NDI-NHC ligand leads to reversible deactivation of the catalyst, providing direct evidence for redox-switchable control of catalytic activity. Kinetic analyses and substrate studies indicate that imine reduction, rather than methanol dehydrogenation, constitutes the rate-determining step. These findings highlight NDI-NHC ligands as versatile redox-responsive platforms for fine-tuning electronic properties and catalytic performance in hydrgen-borrowing transformations.","dates":{"release":"2025-01-01T00:00:00Z","publication":"2025 Dec","modification":"2026-06-06T08:18:14.097Z","creation":"2026-05-27T03:11:52.571Z"},"accession":"S-EPMC12754753","cross_references":{"pubmed":["41381375"],"doi":["10.1021/acs.inorgchem.5c04216"]}}