Complex 2, synthesized by the reaction of {(C₅H₄N)(μ₂–η⁵:η¹-C₉H₅)}Ru₃(CO)₉ (1) with 1,5-hexadiene, could further transform to another diruthenium complex 3via intramolecular carbometalation. The results are relevant to the mechanism of transition-metal catalyzed heteroatom-directed intramolecular C–H/olefin coupling reactions.