Activation of Sulfur- and Nitrogen-Containing Heterocycles by a Dinuclear Iridium Complex

[Cp*IrH3]2 was found to activate both nitrogen- and sulfur-containing heterocycles in the presence of a hydrogen acceptor, giving novel dinuclear organometallic products. In the case of 2-methylthiophene, C−S activation occurred along with a concomitant double hydride transfer and olefin migration to yield a stable adduct. C−H activation α to the heteroatom was observed for N-methylpyrrole, and a pyrrole complex containing a rare Ir−Ir triple bond was also isolated. All heterocycle adducts have been structurally characterized.