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Huo XK, Su G, Jin GX: Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity. Dalton Trans. 2010 Feb 28;39(8):1954-61. Epub 2010 Jan 5.
The neutral Cp*M (Cl)(1-PPh (2)-2-S-1,2-C (2) B (10) H (10)) and zwitterionic Cp*M (3-OCH (3)-7-PPh (2)-8-S-7,8-C (2) B (9) H (9)) (Cp* = eta (5)-C (5) Me (5), M = Ir, Rh, 1-PPh (2)-2-S-1,2-C (2) B (10) H (10) = [1-(diphenylphosphino)-2-thiolato)-1,2-dicarba-closo-carborane], 3-OCH (3)-7-PPh (2)-8-S-7,8-C (2) B (9) H (9) = [3-(methoxyl)-7-(diphenylphosphino)-8-(thiolato)-7,8-dicarba-nido-carboran e](-)) were synthesized and fully characterized. The 18-electron neutral closo-carborane complexes Cp*M (Cl)(1-PPh (2)-2-S-1,2-C (2) B (10) H (10)) (M = Ir (), Rh ()) can be easily deboronated to result in the formation of reactive 16-electron zwitterionic nido-carborane complexes [Cp*M (3-OCH (3)-7-PPh (2)-8-S-7,8-C (2) B (9) H (9))] (M = Ir (), Rh ()). The oxidation of with O (2) gas afforded the corresponding sulfone complex 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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