Synthesis and Structure of Heterometallic Clusters (IrCo2, IrFe) Containing Bridging 1,2-Dicarba-closo-dodecaborane-1,2-dichalocogenolato Ligands

Abstract

The 16-electron half-sandwich iridium complexes [Cp*Ir{E2C2(B10H10)}] [E = S (1a), Se (1b)] (Cp* = η5-C5Me5) [Cp*Ir[E2C2(B10H10)] = η5-pentamethylcyclopentadienyl-[1,2-dicarba-closo-dodecaborane(12)-dichalcogenolato]iridium] reacted with Co2(CO)8 in toluene solution to afford the trinuclear clusters [Cp*Ir{E2C2(B10H10)}]{Co2(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.