Synthesis and deprotonation reactions of halfsandwich iridium complexes bearing av icinal dioxime ligand were studied. Treatment of [{Cp*IrCl(m-Cl)} 2 ]( Cp* = h 5 -C 5 Me 5 ) with dimethylglyoxime (LH 2 )a ta nI r:LH 2 ratio of 1:1a fforded the cationic dioxime iridium complex [Cp*IrCl(LH 2 )]Cl (1). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oximeoximato complex [Cp*IrCl(LH)] (2)a nd the anionic dioximato(2À)c omplex K[Cp*IrCl(L)] (3)s equentially.M eanwhile, twofold deprotonation of the sulfato complex [Cp*Ir(-SO 4 )(LH 2 )] (4)r esulted in the formationo ft he oximatobridgedd inuclear complex [{Cp*Ir(m-L)} 2 ]( 5). X-ray analyses disclosed their supramolecular structures with one-dimensionali nfinite chain (1 and 2), hexagonal open channels (3), and at etrameric rhomboid (4)f eaturing multiple intermolecular hydrogen bonds and electrostatic interactions.

Stepwise and reversible deprotonation of organometallic glyoxime complexes of iridium has been achieved. The juggling of the proton beanbag yielded coordination compounds with a variety of structural motifs in their crystals such as one‐dimensional infinite chains, polymeric hexagonal open channels, and a discrete dinuclear complex. Formation of the diverse supramolecular structures is ascribed to the diprotic nature of the glyoxime ligand, which offers sites for hydrogen bonding in the second coordination sphere as well as coordination to the metal centers. More information can be found in the Full Paper by Shigeki Kuwata et al. on page 72 in Issue 1, 2020 (DOI: 10.1002/asia.201901276).

No abstract