Metalloradicals Supported by a meta-Carborane Ligand.

In this work, a pincer-type complex [Cp*Ir-(SNPh)(SNHPh)(C2 B10 H9 )] (2) was synthesized and its reactivity studied in detail. Interestingly, molecular hydrogen can induce the transformation between the metalloradical [Cp*Ir-(SNPh)2 (C2 B10 H9 )] (5. ) and 2. A mixed-valence complex, [(Cp*Ir)2 -(SNPh)2 (C2 B10 H8 )] (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.