160889 20251017144558.0 doi 10.1002/asia.202401665 sideral 144082 ART-2025-144082 eng González-Lainez, Miguel (orcid)0000-0001-7341-0033 Application of NHC-Based Iridium Pincer Complexes in β-Alkylation of Alcohols and N-Alkylation of Amines: Mechanistic Studies on Precatalyst Activation 2025 Access copy available to the general public Unrestricted The iridium(I) complexes [IrBr(cod)(κC‐tBuImCH2PyCH2NRR’)] (NRR’ = NEt2, NHtBu) have been prepared by reaction of the corresponding functionalized imidazolium salt with the appropriate dinuclear compound [Ir(µ‐OR)(cod)]2 (R = OMe, OEt). These compounds react with H2(g) (5 bar) to afford the pincer iridium(III) dihydrido complexes [IrBrH2(κ3C,N,N’‐tBuImCH2PyCH2NRR’)] in good yields. The complexes [IrBr(cod)(κC‐tBuImCH2PyCH2NRR’)] efficiently catalyzed the β‐alkylation of a series of secondary alcohols and the N‐alkylation of a range of aniline derivatives with primary alcohols, with good selectivities for the β‐alkylated alcohol and monoalkylated secondary amine products, respectively at low catalyst loading typically 0.1 mol% and sub‐stoichiometric amount of base in toluene at 383 K. The pincer iridium(III) dihydrido complexes show a catalytic performance similar to that of the iridium(I) complexes in model alkylation reactions. Mechanistic studies on the activation of the catalytic precursors have shown that both types of complexes have the ability to activate benzyl alcohol through the dearomatization of the pyridine ring by selective deprotonation of the methylene linker between the pyridine and the imidazole‐2‐ylidene fragment. DFT calculations suggest that activation of both catalytic precursors could lead to the common pincer iridium(I) hydrido species [IrH(κ3C,N,N‐tBuImCH2PyCH2NEt2)], which may be key to the borrowing hydrogen reaction mechanism. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00 info:eu-repo/semantics/embargoedAccess by https://creativecommons.org/licenses/by/4.0/deed.es info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Jiménez, M. Victoria (orcid)0000-0002-0545-9107 Modrego, F. Javier Universidad de Zaragoza (orcid)0000-0002-9633-3285 Pérez-Torrente, Jesús J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 20, 9 (2025), e202401665 [15 pp.] Chem. Asian J. Chemistry-An Asian Journal 1861-4728 7036191 http://zaguan.unizar.es/record/160889/files/texto_completo.pdf Versión publicada info:eu-repo/date/embargoEnd/2026-05-02 2970333 http://zaguan.unizar.es/record/160889/files/texto_completo.jpg?subformat=icon icon Versión publicada info:eu-repo/date/embargoEnd/2026-05-02 oai:zaguan.unizar.es:160889 articulos driver 2025-10-17-14:13:48 ARTICLE