Abstract: | Synthesis and deprotonation reactions of half‐sandwich iridium complexes bearing a vicinal dioxime ligand were studied. Treatment of {Cp*IrCl(μ‐Cl)}2] (Cp*=η5‐C5Me5) with dimethylglyoxime (LH2) at an Ir:LH2 ratio of 1:1 afforded the cationic dioxime iridium complex Cp*IrCl(LH2)]Cl ( 1 ). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oxime–oximato complex Cp*IrCl(LH)] ( 2 ) and the anionic dioximato(2?) complex KCp*IrCl(L)] ( 3 ) sequentially. Meanwhile, twofold deprotonation of the sulfato complex Cp*Ir(SO4)(LH2)] ( 4 ) resulted in the formation of the oximato‐bridged dinuclear complex {Cp*Ir(μ‐L)}2] ( 5 ). X‐ray analyses disclosed their supramolecular structures with one‐dimensional infinite chain ( 1 and 2 ), hexagonal open channels ( 3 ), and a tetrameric rhomboid ( 4 ) featuring multiple intermolecular hydrogen bonds and electrostatic interactions. |