Addition of a Grignard reagent to keto-substituted (η5-cyclohexadienyl)Mn(CO)3 complexes leads to the corresponding alcohols in very good yields. After acidic treatment, dehydration occurs, which gives rise to the formation of unprecedented (η5-cyclohexadienyl)Mn(CO)3 complexes substituted by a double bond conjugated to the π system as the major compounds, along with uncoordinated trienones due to the rearrangement of the intermediate carbocation. The structure of one of these η5 complexes has been determined by X-ray crystallography as well as one of the corresponding cationic (η6-arene)Mn(CO)3 complexes formed upon hydride abstraction.
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