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Updated: Jan 6, 2026

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Half-Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible
Taishin Takamura1, Takuya Harada1, Tatsuro Furuta1
1Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 E4-1 O-okayama, Meguro-ku, Tokyo, 152-8552, Japan.
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 -C5 Me5 ) 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 K[Cp*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.
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