Two cyclometalated compounds [Ir IIICl{(2-biphenylene-1,8-naphthyridine-κC,N}(η 5-pentamethylcyclopentadienyl)] (1) and [Ir IIICl{(2-(2-N-Methyl-pyrrolyl-1,8-naphthyridine-κC,N}(η 5-pentamethylcyclopentadienyl)] (2) containing naphthyridine based ligands have been synthesized in high yield. Insertion of SnCl 2 to a terminal Ir-Cl bond of 1 affords the mixed Ir-SnCl 3 compound [Ir IIISnCl 3{(2-biphenylene-1,8-naphthyridine-κC,N}(η 5-pentamethylcyclopentadienyl)] (3). The heterobimetallic compound 3 is shown to be an excellent catalyst for a variety of cyanosilylation reactions. A cooperative mechanism has been proposed which involves the simultaneous activation of aldehyde and cyanide precursor by Sn and unbound naphthyridine nitrogen. © 2012 Springer Science+Business Media, LLC.