RT Journal Article
T1 Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
A1 Buil Juan, M Luisa
A1 Collado Martínez, Alba
A1 Gómez Gallego, María Del Mar
A1 Esteruelas Rodrigo, Miguel Ángel
A1 Sierra Rodríguez, Miguel Ángel
A1 Oñate, Enrique
A1 Nicasio, Antonio
AB 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)(η4-C8H12)]2 (M = Rh (1), Ir (2)) and [M(μ-OH)(η4-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(η4-C8H12){κ1-Npy-(HBMePHI)} (5), and the binuclear species [RhCl(η4-C8H12)]2{μ-Npy,Npy-(HBMePHI)} (6). Under the same conditions, complex 2 affords the iridium counterparts IrCl(η4-C8H12){κ1-Npy-(HBMePHI)} (7) and [IrCl- (η4-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(η4-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 exocyclicisoindoline-N double bond, alcoholysis of a pyridyl-N bond, and opening of the five-membered ring of the isoindoline core
PB ACS
SN 0276-7333
YR 2021
FD 2021-03-31
LK https://hdl.handle.net/20.500.14352/110688
UL https://hdl.handle.net/20.500.14352/110688
LA eng
NO Organometallics 2021, 40, 989−1003
NO Ministerio de Ciencia e Innovación
NO Fundación Ramón Areces
DS Docta Complutense
RD 9 abr 2025