| Sumario: | 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. ©
|
|---|
