Palladium-catalyzed chloride substitution of η⁵-(Chlorocyclohexadienyl)Mn(CO)₃ complexes: An access to novel η⁶-(Arene)Mn(CO)₃⁺ cations

Functionalization of η⁵-(chlorocyclohexadienyl)Mn(CO)₃ complexes was achieved by palladium-catalyzed reactions using Pd₂(dba)₃ in the presence of AsPh₃. Arylation, carbonylation, and substitution by alkyne-, alkene-, and heteroatom-based nucleophiles were performed, giving rise to functionalized η⁵ complexes whose structures have been investigated by NMR and X-ray studies. These η⁵ complexes are valuable precursors upon exo-hydride abstraction, of the corresponding η⁶ cations, substituted by resonance-withdrawing groups, whose conformations in solution and in the solid state have been studied.