Preparation and Degradation of Rhodium and Iridium Diolefin Catalysts for the Acceptorless and Base-Free Dehydrogenation of Secondary Alcohols

[Image: see text] 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)(η(4)-C(8)H(12))](2) (M = Rh (1), Ir (2)) and [M(μ-OH)(η(4)-C(8)H(12))](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(η(4)-C(8)H(12)){κ(1)-N(py)-(HBMePHI)} (5), and the binuclear species [RhCl(η(4)-C(8)H(12))](2){μ-N(py),N(py)-(HBMePHI)} (6). Under the same conditions, complex 2 affords the iridium counterparts IrCl(η(4)-C(8)H(12)){κ(1)-N(py)-(HBMePHI)} (7) and [IrCl(η(4)-C(8)H(12))](2){μ-N(py),N(py)-(HBMePHI)} (8). In contrast to chloride, one of the hydroxide groups of 3 and 4 promotes the deprotonation of HBMePHI to give [M(η(4)-C(8)H(12))](2)(μ-OH){μ-N(py),N(iso)-(BMePHI)} (M = Rh (9), Ir (10)), which are efficient precatalysts for the acceptorless and base-free dehydrogenation of secondary alcohols. In the presence of KO(t)Bu, 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.