131711 20241125101141.0 doi 10.1021/acs.organomet.3c00403 sideral 137253 ART-2023-137253 eng González-Lainez, Miguel (orcid)0000-0001-7341-0033 Rhodium and iridium complexes of lutidine-based NHC/Amino Pincer ligands: From monodentate to tetradentate coordination enabled by C–H activation 2023 Access copy available to the general public Unrestricted A series of rhodium and iridium complexes derived from lutidine-based ligands (lutidine, 2,6-dimethylpyridine) with NHC and amino side-donor functions have been prepared and characterized. Deprotonation of the functionalized imidazolium salts, [tBuHImCH2PyCH2NR2]Br, by the bridging methoxo ligands of the dinuclear complexes [M(μ-OMe)(cod)]2 affords [MBr(cod)(κC-tBuImCH2PyCH2NR2)] (M = Rh and Ir) complexes from which a series of Rh(I) and Ir(I) complexes including [M(cod)(κ3C,N,N′-tBuImCH2PyCH2NR2)]+, [Rh(CO)(κ3C,N,N′-tBuImCH2PyCH2NR2)]+, and [IrBr(CO)2(κC-tBuImCH2PyCH2NR2)] are readily accessible by halide abstraction and/or carbonylation reactions. In contrast, direct metalation of imidazolium salts with the dinuclear compounds [M(μ-Cl)(cod)]2 (M = Rh and Ir) in the presence of potassium acetate and potassium iodide, a well-established synthetic route to M(III) species, provides access to unusual di-iodido M(III) cyclometalated compounds [MI2{κ4C,C′,N,N′-(CH2CMe2ImCH2PyCH2NR2)}] in low yield. Experimental studies combined with DFT calculations suggest that cyclometalated M(III) hydrido [MH(CH3CN){κ4C,C′,N,N′-(CH2CMe2ImCH2PyCH2NR2)}]+ compounds and square-planar cyclometalated M(I) [M{κ4C,C′,N,N′-(CH2CMe2ImCH2PyCH2NR2)}] species resulting from their deprotonation by acetate could be intermediates involved in the formation of these compounds. Based on the observed formation of elemental rhodium, disproportionation of square-planar cyclometalated M(I) complexes to afford M(0) and the cationic M(II) species [M{κ4C,C′,N,N′-(CH2CMe2ImCH2PyCH2NR2)}]+ is proposed. Reaction of the latter with iodide (I–) would regenerate the M(I) intermediate to give an iodo radical (I•) that in turn could dimerize to form diiodine I2. In this regard, DFT calculations have shown that the oxidative addition of diiodine to the cyclometalated M(I) intermediates leading to the di-iodido M(III) cyclometalated compounds is a highly exergonic process. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033 info:eu-repo/grantAgreement/ES/MINECO/BES-2014-069624 info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 2.5 2023 CHEMISTRY, ORGANIC 16 / 58 = 0.276 2023 Q2 T1 CHEMISTRY, INORGANIC & NUCLEAR 21 / 44 = 0.477 2023 Q2 T2 0.654 2023 Inorganic Chemistry 2023 Q1 Physical and Theoretical Chemistry 2023 Q2 Organic Chemistry 2023 Q2 5.6 2023 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Jiménez, M. Victoria (orcid)0000-0002-0545-9107 Passarelli, Vincenzo (orcid)0000-0002-1735-6439 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 42, 22 (2023), 3292-3306 Organometallics Organometallics 0276-7333 3658361 http://zaguan.unizar.es/record/131711/files/texto_completo.pdf Versión publicada 2916290 http://zaguan.unizar.es/record/131711/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:131711 articulos driver 2024-11-22-12:02:39 ARTICLE