Structure and Reactivity of a Pyridine-1-imido-2-thiolato Complex of Iridium(III), Cp*Ir(1-N-2-Spy), Generated by Photolysis of the (Azido)(pyridine-2-thiolato) Complex, Cp*Ir(2-Spy)(N₃)

Photolysis of the (azido)(pyridine-2-thiolato)iridium(III) complex Cp*Ir(2-Spy)(N3) (1) gave a pyridine-1-imido-2-thiolato complex, Cp*Ir(1-N-2-Spy) (2), in which one of the nitrogen atoms of the azide ligand has been inserted into the Ir−N(py) bond (Cp* = η5-C5Me5). Complex 2 reacted quantitatively with methyl iodide to give the N-methylated product, [Cp*Ir(1-NMe-2-Spy)]I (3). X-ray crystallography revealed that both 2 and 3 have similar two-legged piano stool structures with planar 1-N-2-Spy2- or 1-NMe-2-Spy- ligands, which form iridacyclopentadienyl-like rings by moderate S(pπ)/N(pπ) to Ir(dπ) π donation.