Synthesis and structure of heterometallic clusters (IrCo2, IrFe) containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalocogenolato ligands

The 16-electron half-sandwich iridium complexes [Cp*Ir{E2C2(B10H10)}] [E = S (1a), Se (1b)] (Cp* = eta(5)-C5Me5) [Cp*Ir[E2C2(B10H10)] = eta(5)-pentamethylcyclopentadienyl-[1,2-dicarbacloso-dodecaborane(12)-dichalcogenolato]iridium] reacted with Co-2(CO)(8) in toluene solution to afford the trinuclear clusters [Cp*Ir{E2C2(B10H10)}]{Co-2(CO)(5)} [E = S (2a), Se (2b)] and mononuclear complexes [Cp*Ir(CO){E2C2(B10H10)}] [E = S (3a), Se (3b)] as byproducts. Compounds 2a and 2b contain closed IrCo2 triangle geometry with one Co-Co and two Ir-Co bonds. The dinuclear IrFe complexes [Cp*Ir{E2C2(B10H10)}]{Fe(CO)(3)} [E = S (4a), Se (4b)] were obtained from the reactions of 1a and 1b with Fe(CO)5 in the presence of Me3NO. The molecular structures of 2a, 2b, and 4b have been determined by X-ray crystallography.