Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity.
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-carborane](-)) 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.
Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Advanced Materials Laboratory, Fudan University, 200433, Shanghai, PR China.
Xian-Kuan
XK
Huo
Ge
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Su
Guo-Xin
GX
Jin