The neutral Cp*M(Cl)(1-PPh2-2-S-1,2-C2B10H10) and zwitterionic Cp*M(3-OCH3-7-PPh2-8-S-7,8-C2B9H9) (Cp* = η5-C5Me5, M = Ir, Rh, 1-PPh2-2-S-1,2-C2B10H10 = [1-(diphenylphosphino)-2-thiolato)-1,2-dicarba-closo-carborane], 3-OCH3-7-PPh2-8-S-7,8-C2B9H9 = [3-(methoxyl)-7-(diphenylphosphino)-8-(thiolato)-7,8-dicarba-nido-carborane]−) were synthesized and fully characterized. The 18-electron neutral closo-carborane complexes Cp*M(Cl)(1-PPh2-2-S-1,2-C2B10H10) (M = Ir (1a), Rh (1b)) can be easily deboronated to result in the formation of reactive 16-electron zwitterionic nido-carborane complexes [Cp*M(3-OCH3-7-PPh2-8-S-7,8-C2B9H9)] (M = Ir (2a), Rh(2b)). The oxidation of 2b with O2 gas afforded the corresponding sulfone complex 3b in high yields. Utilization of its unsaturated feature in 16-electron zwitterionic nido-carborane complexes offers a potential strategy to synthesize new types of organometallic complexes.
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