Rhenabenzenes and Unexpected Coupling Products from the Reactions of Rhenacyclobutadienes with Ethoxyethyne

Treatment of Na­[Re­(CO)₅] with methyl 3-(naphthalen-1-yl)­propiolate (NpCCCO₂Me) followed by acetyl chloride and alcohols ROH (R = Me, ⁿPr) afforded the rhenacyclobutadiene complexes Re­{-C­(Np)C­(CO₂Me)­C­(OR)}­(CO)₄. Reactions of these rhenacyclobutadiene complexes with HCCOEt produced the rhenabenzene complexes Re­{-C­(Np)C­(CO₂Me)­C­(OR)CHC­(OEt)}­(CO)₄ and new rhenacyclobutadienes with a pendant vinyl substituent Re­{-C­(Np)C­(C­(OR)CH­(CO₂Et))­C­(OMe)}­(CO)₄. In the vinyl-substituted rhenacyclobutadiene products, the ethyl of the ester group is from the alkyne HCCOEt, the alkyl of the ReC­(OR) group is from the ester group of the starting rhenacyclobutadienes, and the alkyl group of the OR of the vinyl substituent is from the ReC­(OR) group of the starting rhenacyclobutadienes. A plausible mechanism for the formation of the vinyl-substituted rhenacyclobutadienes is discussed.