Structure and Reactivity of a Pyridine-1-imido-2-thiolato Complex of Iridium(III),Cp*lr(1-N-2-Spy),Generated by Photolysis of the (Azido)(pyridine-2-thiolato) Complex,Cp*Ir(2-Spy)(N_3)

摘要

Photolysis of the (azido)(pyridine-2-thiolato)iridium(III) complex Cp*Ir(2-Spy)(N_3) (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*=eta~5-C_5Me5).Complex 2 reacted quantitatively with methyl iodide to give the N-methylated product,[Cp*Ir(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-Spy~- ligands,which form iridacyclopentadienyl-like rings by moderate S(ppi)/N(ppi) to Ir(dpi) pi donation.