Reaction of Organolithium Reagents with Cyclorhenated and Cyclomanganated (η<b>⁶</b>-Arene)tricarbonylchromium Complexes: Structural Characterization of a New Benzoylrhenate Intermediate and Selective Ortho-Acetylation of (η⁶-Arene)tricarbonylchromium Complexes

The nucleophilic addition of PhLi to tetracarbonyl[3-methyl-2-{(η6-phenyl)tricarbonylchromium(0)}pyridine]rhenium(I) yields the air-stable (exo-benzoyl)(tricarbonyl)[3-methyl-2-{(η6-phenyl)tricarbonylchromium(0)-κC2‘}pyridine-κN]rhenate(I) that has been isolated and characterized by X-ray diffraction analysis and other spectroscopic methods. A similar treatment applied to cyclomanganated (η6-arene)Cr(CO)3 analogues with a nucleophile such as MeLi provides a new route to the synthesis of ortho disubstituted (η6-acetophenone)Cr(CO)3 derivatives.