000171047 001__ 171047
000171047 005__ 20260505142650.0
000171047 0247_ $$2doi$$a10.1021/acs.inorgchem.6c01357
000171047 0248_ $$2sideral$$a149158
000171047 037__ $$aART-2026-149158
000171047 041__ $$aeng
000171047 100__ $$0(orcid)0000-0002-1430-1440$$aBatuecas, Maria$$uUniversidad de Zaragoza
000171047 245__ $$aMethylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N-Alkylation
000171047 260__ $$c2026
000171047 5060_ $$aAccess copy available to the general public$$fUnrestricted
000171047 5203_ $$aWe 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.
000171047 536__ $$9info:eu-repo/grantAgreement/EC/H2020/101034288/EU/International Fellowship Programme for Talent Attraction to the Campus of International Excellence Campus Iberus/IberusExperience$$9This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 101034288-IberusExperience
000171047 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000171047 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000171047 700__ $$aGarcia, Beatriz
000171047 700__ $$aSaviozzi, Chiara
000171047 700__ $$aViana, Maria S.
000171047 700__ $$aMaseras, Feliu
000171047 700__ $$aRoyo, Beatriz
000171047 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000171047 773__ $$g65, 16 (2026), 9265-9273$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000171047 8564_ $$s3390360$$uhttps://zaguan.unizar.es/record/171047/files/texto_completo.pdf$$yVersión publicada
000171047 8564_ $$s3048345$$uhttps://zaguan.unizar.es/record/171047/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000171047 909CO $$ooai:zaguan.unizar.es:171047$$particulos$$pdriver
000171047 951__ $$a2026-05-05-13:36:31
000171047 980__ $$aARTICLE