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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.

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