Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Advanced Materials Laboratory, Fudan University, 200433, Shanghai, PR China.
Dalton Trans. 2010 Feb 28;39(8):1954-61. doi: 10.1039/b918272a. Epub 2010 Jan 5.
The neutral CpM(Cl)(1-PPh(2)-2-S-1,2-C(2)B(10)H(10)) and zwitterionic CpM(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 CpM(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 [CpM(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.
中性 CpM(Cl)(1-PPh(2)-2-S-1,2-C(2)B(10)H(10)) 和两性离子 CpM(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-(二苯基膦基)-2-硫代]-1,2-二碳杂-closo-卡硼烷], 3-OCH(3)-7-PPh(2)-8-S-7,8-C(2)B(9)H(9)=3-(甲氧基)-7-(二苯基膦基)-8-(硫代)-7,8-二碳杂-nido-卡硼烷）被合成并进行了充分的表征。18 电子中性 closo-卡硼烷配合物 CpM(Cl)(1-PPh(2)-2-S-1,2-C(2)B(10)H(10))（M=Ir()，Rh()）很容易脱硼，形成反应性的 16 电子两性离子 nido-卡硼烷配合物 [CpM(3-OCH(3)-7-PPh(2)-8-S-7,8-C(2)B(9)H(9))]（M=Ir()，Rh()）。用 O(2)气体氧化得到相应的砜配合物，产率很高。利用其在 16 电子两性离子 nido-卡硼烷配合物中的不饱和特性，为合成新型金属有机配合物提供了一种潜在的策略。
