Reaction of tetracarbonyl[2‐{(η6‐phenyl)tricarbonylchromium‐ĸC2′}pyridine‐ĸN]manganese(I), 2a, with phenyllithium quantitatively affords an acylmanganese anion 3a that can be isolated and spectroscopically characterized. In‐situ O‐alkylation of the latter anion by means of MeOSO2CF3 at low temperature, yields a new neutral syn‐facial heterobimetallic analog 4a of (η5‐cyclohexadienyl)benzylidene complexes. The treatment of bimetallic carbonyl complexes of 3‐methyl, 2‐phenyl‐pyridine and 2‐phenyl‐quinoline, 2b and 2c, with PhLi and subsequently with MeOSO2CF3 affords deep purple crystalline products 4b and 4c that have been structurally characterized by X‐ray diffraction analyses. The molecular structures of 4b and 4c display, among other features, an overall helical shape with a pronounced π‐stacking of the aromatic groups and a weak interaction between the chromium and the manganese centeredunits.

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