171047 20260505142650.0 doi 10.1021/acs.inorgchem.6c01357 sideral 149158 ART-2026-149158 eng Batuecas, Maria Universidad de Zaragoza (orcid)0000-0002-1430-1440 Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation 2026 We elucidate the mechanism of the manganese-catalyzed N-alkylation of aniline with benzyl alcohol mediated by a bis(1,2,3-triazolylidene) Mn(I) complex through a combination of experimental studies and density functional theory (DFT) calculations. Activation of the precatalyst by a base leads to the formation of an anionic alkoxo complex featuring a deprotonated methylene bridge, which is identified as the catalytically active species. Notably, the methylene linker exhibits previously unrecognized noninnocent behavior, undergoing reversible deprotonation and participating directly in proton-transfer steps of the catalytic cycle. Kinetic isotope effects and deuterium-labeling experiments support the involvement of both hydride transfer and alcohol-assisted proton processes in the rate-determining steps. These findings uncover a new mode of metal–ligand cooperation in triazolylidene-based manganese catalysts and provide mechanistic guidelines for the design of cooperative ligands in base-metal-borrowing hydrogen catalysis. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/EC/H2020/101034288/EU/International Fellowship Programme for Talent Attraction to the Campus of International Excellence Campus Iberus/IberusExperience This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 101034288-IberusExperience info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Garcia, Beatriz Saviozzi, Chiara Viana, Maria S. Maseras, Feliu Royo, Beatriz 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 65, 16 (2026), 9265-9273 Inorg. chem. Inorganic Chemistry 0020-1669 3390360 http://zaguan.unizar.es/record/171047/files/texto_completo.pdf Versión publicada 3048345 http://zaguan.unizar.es/record/171047/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:171047 articulos driver 2026-05-05-13:36:31 ARTICLE