Metallapentalenofuran: Shifting Metallafuran Rings Promoted by Substituent Effects

Bulky substituents play important roles in controlling the reaction pathways or producing selected products. This work reports that the shift of metallafuran rings in a metallapentalenofuran complex can be promoted by the substituent effect via a reversible C−H bond reductive elimination and oxidative addition. The starting osmapentalyne, a so‐called 7‐carbon carbolong complex, was produced by the oxidation of a metallapentalenofuran with FeCl 3 . It was then allowed to react with nucleophiles, followed by a C−H activation, to give the aforementioned metallapentalenofuran complex. This work enriches the family of carbolong complexes and reveals a new strategy to promote, but not prevent reactions by the bulky substituents.