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. Metal to metal: The metalloradical species [(Cp*Ir)2‐(SNPh)2(C2B10H8)] and [Cp*Ir‐(SNPh)2(C2B10H9)], based on carborane backbone ligands, have been synthesized by oxidation with I2 and loss of H2, respectively. Evidence indicates that the mixed‐valence [(Cp*Ir)2‐(SNPh)2(C2B10H8)] is fully delocalized, possessing a four‐centered‐one‐electron (S‐Ir‐Ir‐S) bonding interaction. Interestingly, molecular hydrogen can induce the reverse transformation of the neutral radical [Cp*Ir‐(SNPh)2(C2B10H9)].