Novel iron-aroyl complexes or synthetically prized arylcyclohexadienyl complexes can be formed from tricarbonyl(η 5 -1,4-dimethoxycyclohexadienyl)iron(1+) hexafluorophosphate(1-) by correct control of reaction sequences that exploit the addition of aryllithium reagents to introduce the aromatic group. Bimetallic products are obtained when a tricarbonylchromium-bound aryllithium reagent or the corresponding cuprate are employed.