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)] [ (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-Spy ^- ligands, which form iridacyclopentadienyl-like rings by moderate S(pπ)/N(pπ) to Ir(dπ) π donation.