Metalloradicals Supported by a meta-Carborane Ligand

In this work, a pincer-type complex [Cp*Ir-(SNPh)(SNHPh)(C2B10H9)] (2) was synthesized and its reactivity studied in detail. Interestingly, molecular hydrogen can induce the transformation between the metalloradical [Cp*Ir-(SNPh)(2)(C2B10H9)] (5(.)) and 2. A mixed-valence complex, [(Cp*Ir)(2)-(SNPh)(2)(C2B10H8)] (7(.+)), was also synthesized by one-electron oxidation. Studies show that 7(.+) is fully delocalized, possessing a four-centered-one-electron (S-Ir-Ir-S) bonding interaction. DFT calculations were also in good agreement with the experimental results.