New tris(4,4-dimethyl-2-oxazolinyl)phenylboratoiridium(I) scorpionate-type compounds [Ir(ToM)L2] (L2=η4-C8H12 and (CO)2) and electrophiles form adducts that contain a bidentate IrToM-coordination and an N–electrophile interaction of the third oxazoline instead of the oxidative addition product. The adduct with lithium chloride gives a unique heterobimetallic Li–O-oxazoline-N–Ir bridging structure that has been identified through X-ray crystallography. Density functional theory calculations provide thermodynamic data, orbital symmetries, and orbital energies that explain the formation of the observed iridium(I) products.