000131711 001__ 131711
000131711 005__ 20241125101141.0
000131711 0247_ $$2doi$$a10.1021/acs.organomet.3c00403
000131711 0248_ $$2sideral$$a137253
000131711 037__ $$aART-2023-137253
000131711 041__ $$aeng
000131711 100__ $$0(orcid)0000-0001-7341-0033$$aGonzález-Lainez, Miguel
000131711 245__ $$aRhodium and iridium complexes of lutidine-based NHC/Amino Pincer ligands: From monodentate to tetradentate coordination enabled by C–H activation
000131711 260__ $$c2023
000131711 5060_ $$aAccess copy available to the general public$$fUnrestricted
000131711 5203_ $$aA series of rhodium and iridium complexes derived from lutidine-based ligands (lutidine, 2,6-dimethylpyridine) with NHC and amino side-donor functions have been prepared and characterized. Deprotonation of the functionalized imidazolium salts, [tBuHImCH2PyCH2NR2]Br, by the bridging methoxo ligands of the dinuclear complexes [M(μ-OMe)(cod)]2 affords [MBr(cod)(κC-tBuImCH2PyCH2NR2)] (M = Rh and Ir) complexes from which a series of Rh(I) and Ir(I) complexes including [M(cod)(κ3C,N,N′-tBuImCH2PyCH2NR2)]+, [Rh(CO)(κ3C,N,N′-tBuImCH2PyCH2NR2)]+, and [IrBr(CO)2(κC-tBuImCH2PyCH2NR2)] are readily accessible by halide abstraction and/or carbonylation reactions. In contrast, direct metalation of imidazolium salts with the dinuclear compounds [M(μ-Cl)(cod)]2 (M = Rh and Ir) in the presence of potassium acetate and potassium iodide, a well-established synthetic route to M(III) species, provides access to unusual di-iodido M(III) cyclometalated compounds [MI2{κ4C,C′,N,N′-(CH2CMe2ImCH2PyCH2NR2)}] in low yield. Experimental studies combined with DFT calculations suggest that cyclometalated M(III) hydrido [MH(CH3CN){κ4C,C′,N,N′-(CH2CMe2ImCH2PyCH2NR2)}]+ compounds and square-planar cyclometalated M(I) [M{κ4C,C′,N,N′-(CH2CMe2ImCH2PyCH2NR2)}] species resulting from their deprotonation by acetate could be intermediates involved in the formation of these compounds. Based on the observed formation of elemental rhodium, disproportionation of square-planar cyclometalated M(I) complexes to afford M(0) and the cationic M(II) species [M{κ4C,C′,N,N′-(CH2CMe2ImCH2PyCH2NR2)}]+ is proposed. Reaction of the latter with iodide (I–) would regenerate the M(I) intermediate to give an iodo radical (I•) that in turn could dimerize to form diiodine I2. In this regard, DFT calculations have shown that the oxidative addition of diiodine to the cyclometalated M(I) intermediates leading to the di-iodido M(III) cyclometalated compounds is a highly exergonic process.
000131711 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E42-23R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033$$9info:eu-repo/grantAgreement/ES/MINECO/BES-2014-069624
000131711 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000131711 590__ $$a2.5$$b2023
000131711 592__ $$a0.654$$b2023
000131711 591__ $$aCHEMISTRY, ORGANIC$$b16 / 58 = 0.276$$c2023$$dQ2$$eT1
000131711 593__ $$aInorganic Chemistry$$c2023$$dQ1
000131711 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b21 / 44 = 0.477$$c2023$$dQ2$$eT2
000131711 593__ $$aPhysical and Theoretical Chemistry$$c2023$$dQ2
000131711 593__ $$aOrganic Chemistry$$c2023$$dQ2
000131711 594__ $$a5.6$$b2023
000131711 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000131711 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M. Victoria
000131711 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, Vincenzo
000131711 700__ $$0(orcid)0000-0002-9633-3285$$aModrego, F. Javier$$uUniversidad de Zaragoza
000131711 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, Jesús J.$$uUniversidad de Zaragoza
000131711 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000131711 773__ $$g42, 22 (2023), 3292-3306$$pOrganometallics$$tOrganometallics$$x0276-7333
000131711 8564_ $$s3658361$$uhttps://zaguan.unizar.es/record/131711/files/texto_completo.pdf$$yVersión publicada
000131711 8564_ $$s2916290$$uhttps://zaguan.unizar.es/record/131711/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000131711 909CO $$ooai:zaguan.unizar.es:131711$$particulos$$pdriver
000131711 951__ $$a2024-11-22-12:02:39
000131711 980__ $$aARTICLE