119659 20251219150009.0 doi 10.1021/acs.organomet.1c00068 sideral 126640 ART-2021-126640 eng Buil M.L. Universidad de Zaragoza (orcid)0000-0002-3284-1053 Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols 2021 Access copy available to the general public Unrestricted Rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols have been prepared, and their degradation has been investigated, during the study of the reactivity of the dimers [M(µ-Cl)(I4-C8H12)]2 (M = Rh (1), Ir (2)) and [M(µ-OH)(I4-C8H12)]2 (M = Rh (3), Ir (4)) with 1, 3-bis(6'-methyl-2'-pyridylimino)isoindoline (HBMePHI). Complex 1 reacts with HBMePHI, in dichloromethane, to afford equilibrium mixtures of 1, the mononuclear derivative RhCl(I4-C8H12){¿1-Npy-(HBMePHI)} (5), and the binuclear species [RhCl(I4-C8H12)]2{µ-Npy, Npy-(HBMePHI)} (6). Under the same conditions, complex 2 affords the iridium counterparts IrCl(I4-C8H12){¿1-Npy-(HBMePHI)} (7) and [IrCl(I4-C8H12)]2{µ-Npy, Npy-(HBMePHI)} (8). In contrast to chloride, one of the hydroxide groups of 3 and 4 promotes the deprotonation of HBMePHI to give [M(I4-C8H12)]2(µ-OH){µ-Npy, Niso-(BMePHI)} (M = Rh (9), Ir (10)), which are efficient precatalysts for the acceptorless and base-free dehydrogenation of secondary alcohols. In the presence of KOtBu, the [BMePHI]- ligand undergoes three different degradations: Alcoholysis of an exocyclic isoindoline-N double bond, alcoholysis of a pyridyl-N bond, and opening of the five-membered ring of the isoindoline core. © info:eu-repo/grantAgreement/ES/DGA/E06-17R info:eu-repo/grantAgreement/ES/MICINN/PID2019-108429RB-I00 info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es 3.837 2021 CHEMISTRY, ORGANIC 15 / 56 = 0.268 2021 Q2 T1 CHEMISTRY, INORGANIC & NUCLEAR 12 / 46 = 0.261 2021 Q2 T1 0.994 2021 Organic Chemistry 2021 Q1 Inorganic Chemistry 2021 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Collado A. Esteruelas M.A. (orcid)0000-0002-4829-7590 Gomez-Gallego M. Izquierdo S. Universidad de Zaragoza (orcid)0000-0002-6608-1910 Iglesias Nicasio A. Oñate E. (orcid)0000-0003-2094-719X Sierra M.A. 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 40, 7 (2021), 989-1003 Organometallics Organometallics 0276-7333 3565586 http://zaguan.unizar.es/record/119659/files/texto_completo.pdf Versión publicada 2828245 http://zaguan.unizar.es/record/119659/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:119659 articulos driver 2025-12-19-14:58:11 ARTICLE