Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols

Buil M.L. (Universidad de Zaragoza) ; Collado A. ; Esteruelas M.A. ; Gomez-Gallego M. ; Izquierdo S. (Universidad de Zaragoza) ; Iglesias Nicasio A. ; Oñate E. ; Sierra M.A.

Resumen: 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. ©

Idioma: Inglés

DOI: 10.1021/acs.organomet.1c00068

Año: 2021

Publicado en: Organometallics 40, 7 (2021), 989-1003
ISSN: 0276-7333

Factor impacto JCR: 3.837 (2021)

Categ. JCR: CHEMISTRY, ORGANIC rank: 15 / 57 = 0.263 (2021) - Q2 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 12 / 46 = 0.261 (2021) - Q2 - T1

Factor impacto SCIMAGO: 0.994 - Organic Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E06-17R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2019-108429RB-I00
Financiación: info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)