Incorporation of Monatomic Cations onto an Ir–Ir Bond in a Dimeric Iridium(II) Complex Having a 1,3-Diene-1,4-diyl Backbone

A dinuclear iridium­(II) complex with 1,3-butadiene-1,4-diyl backbone and iridium–iridium bonding interaction has been found from the complexation of an iridium­(I) precursor and an alkyne-containing bisphosphine ligand. This complex shows binding ability toward a variety of cations such as Ag+, I+, H+ to afford merged cationic diiridium complexes. Structural differences and electronic features of iridium–iridium bonding are discussed using X-ray crystallographic analyses as well as in silico studies with density functional theory.