Photolysis of the (azido)(pyrdine-2-thiolato)iridium(III) complex Cp*lr(2-Spy)(N-3) (1) gave a pyridine-1-imido-2-thiolato complex, Cp*lr(1-N-2-Spy) (2), in which one of the nitrogen atoms of the azide ligand has been inserted into the lr-N(py) bond (Cp* = eta(5)-C5Me5). Complex 2 reacted quantitatively with methyl iodide to give the N-methylated product, [Cp*lr(1-NMe-2-Spy)]l (3). X-ray crystallography revealed that both 2 and 3 have similar two-legged piano stool structures with planar 1-N-2-Spy(2-) or 1-NMe-2(-)Spyligands, which form iridacyclopentadienyl-like rings by moderate S(p pi)/N(p pi) to lr(d pi) pi donation.