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 alpha 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.