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These compounds react with H<jats:sub>2<\/jats:sub>(g) (5 bar) to afford the pincer iridium(III) dihydrido complexes [IrBrH<jats:sub>2<\/jats:sub>(\u03ba<jats:sup>3<\/jats:sup><jats:italic>C<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>N\u2019<\/jats:italic>\u2010<jats:italic><jats:sup>t<\/jats:sup><\/jats:italic>BuImCH<jats:sub>2<\/jats:sub>PyCH<jats:sub>2<\/jats:sub>NRR\u2019)] in good yields. The complexes [IrBr(cod)(\u03ba<jats:italic>C<\/jats:italic>\u2010<jats:italic><jats:sup>t<\/jats:sup><\/jats:italic>BuImCH<jats:sub>2<\/jats:sub>PyCH<jats:sub>2<\/jats:sub>NRR\u2019)] efficiently catalyzed the <jats:italic>\u03b2<\/jats:italic>\u2010alkylation of a series of secondary alcohols and the <jats:italic>N<\/jats:italic>\u2010alkylation of a range of aniline derivatives with primary alcohols, with good selectivities for the <jats:italic>\u03b2<\/jats:italic>\u2010alkylated alcohol and monoalkylated secondary amine products, respectively at low catalyst loading typically 0.1 mol% and sub\u2010stoichiometric 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\u20102\u2010ylidene fragment. DFT calculations suggest that activation of both catalytic precursors could lead to the common pincer iridium(I) hydrido species [IrH(\u03ba<jats:sup>3<\/jats:sup><jats:italic>C<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010<jats:italic><jats:sup>t<\/jats:sup><\/jats:italic>BuImCH<jats:sub>2<\/jats:sub>PyCH<jats:sub>2<\/jats:sub>NEt<jats:sub>2<\/jats:sub>)], which may be key to the borrowing hydrogen reaction mechanism.<\/jats:p>","DOI":"10.1002\/asia.202401665","type":"journal-article","created":{"date-parts":[[2025,3,12]],"date-time":"2025-03-12T00:16:19Z","timestamp":1741738579000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Application of NHC\u2010Based Iridium Pincer Complexes in <i>\u03b2<\/i>\u2010Alkylation of Alcohols and <i>N<\/i>\u2010Alkylation of Amines: Mechanistic Studies on Precatalyst Activation"],"prefix":"10.1002","volume":"20","author":[{"given":"Miguel","family":"Gonz\u00e1lez\u2010Lainez","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea\u2010ISQCH Universidad de Zaragoza\u2010C.S.I.C  C\/ Pedro Cebuna, 12 Zaragoza 50009 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"M. Victoria","family":"Jim\u00e9nez","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea\u2010ISQCH Universidad de Zaragoza\u2010C.S.I.C  C\/ Pedro Cebuna, 12 Zaragoza 50009 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"F. Javier","family":"Modrego","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea\u2010ISQCH Universidad de Zaragoza\u2010C.S.I.C  C\/ Pedro Cebuna, 12 Zaragoza 50009 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jes\u00fas J.","family":"P\u00e9rez\u2010Torrente","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea\u2010ISQCH Universidad de Zaragoza\u2010C.S.I.C  C\/ Pedro Cebuna, 12 Zaragoza 50009 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,4,14]]},"reference":[{"key":"e_1_2_10_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.4c00094"},{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.1c00125"},{"key":"e_1_2_10_2_2","author":"Alexandridis A.","year":"2024","journal-title":"ChemCatChem"},{"key":"e_1_2_10_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00340"},{"key":"e_1_2_10_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CS00496E"},{"key":"e_1_2_10_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202200474"},{"key":"e_1_2_10_4_3","doi-asserted-by":"publisher","DOI":"10.1039\/D2OB00706A"},{"key":"e_1_2_10_4_4","doi-asserted-by":"publisher","DOI":"10.1039\/D3CC01517C"},{"key":"e_1_2_10_4_5","doi-asserted-by":"publisher","DOI":"10.1039\/D4CC00003J"},{"key":"e_1_2_10_4_6","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-024-49249-2"},{"key":"e_1_2_10_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1QO01412A"},{"key":"e_1_2_10_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c03957"},{"key":"e_1_2_10_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202400291"},{"key":"e_1_2_10_5_4","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202304205"},{"key":"e_1_2_10_5_5","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.4c01561"},{"key":"e_1_2_10_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00306"},{"key":"e_1_2_10_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8OB01895B"},{"key":"e_1_2_10_6_3","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c03440"},{"key":"e_1_2_10_6_4","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2024.134192"},{"key":"e_1_2_10_6_5","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.20.98"},{"key":"e_1_2_10_6_6","doi-asserted-by":"publisher","DOI":"10.1039\/D4QO01626B"},{"key":"e_1_2_10_6_7","doi-asserted-by":"publisher","DOI":"10.1039\/D4DT01481B"},{"key":"e_1_2_10_6_8","doi-asserted-by":"publisher","DOI":"10.1002\/asia.202400811"},{"key":"e_1_2_10_6_9","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c05889"},{"key":"e_1_2_10_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CY01170H"},{"key":"e_1_2_10_7_2","doi-asserted-by":"crossref","unstructured":"b)S. 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