Structural comparison of (pentamethylcyclopentadienyl)iridium(III) azido complexes containing potentially N,S-bidentate N-heterocyclic thiolates: 2- or 8-quinolinethiolate and benzimidazole-2-thiolate

The crystal structures of mononuclear (azido)(pentamethylcyclopentadienyl)iridium(III) complexes bearing 2- or 8-quinolinethiolate (n-Sqn^-), [Cp^*Ir(N₃)(n-Sqn)] {n = 2 (1) or 8 (2); Cp^* = η⁵-C₅Me₅} have been determined by X-ray analysis. The 2-Sqn complex, 1, acquires severe steric strains in the four-membered κ²N,S chelate ring, while the 8-Sqn isomer, 2, forms a strain-free five-membered planar κ²N,S chelate ring. It has also been revealed that the corresponding benzimidazole-2-thiolate (Hbimt^-) complex, which was obtained similarly to the above n-Sqn complexes from [Cp^*Ir(N₃)₂]₂ and Na(Hbimt), takes an unsymmetrical dinuclear structure bridged by two Hbimt^- ligands with different bonding modes, [Cp^*Ir(N₃){μ(S:N¹)-Hbimt}{μ(S:S)-Hbimt}Ir(N₃)Cp^*] · MeOH (3).