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Synthesis and Structure of Half-Sandwich Pyridine-2-thiolato Cobalt(III) and Rhodium(III) Complexes and Their Reactivity toward Monodentate or Bidentate 1,2-Dicarba-closo-dodecaborane Thiolate Ligands

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journal contribution
posted on 25.02.2008, 00:00 by Shu Liu, Hui Wang, Peng-Cheng Zhang, Lin-Hong Weng, Xiu-Feng Hou
The half-sandwich cobalt(III) and rhodium(III) complexes with pyridine-2-thiolato ligands Cp*Co(PyS)I (3) and Cp*Rh(PyS)Cl (4) [Cp* = pentamethylcyclopentadienyl, PyS = pyridine-2-thiolate] were obtained by reactions of lithium pyridine-2-thiolate (PySLi) with Cp*Co(CO)I2 (1) and [Cp*RhCl2]2 (2), respectively, in high yield. Complexes 3 and 4 reacted with monodentate LiSC2(H)B10H10 to give Cp*Co(PyS)[SC2(H)B10H10] (5) and Cp*Rh(PyS)[SC2(H)B10H10] (6), respectively. Reactions of 3 and 4 with Li2S2C2B10H10 resulted in C−H activation of a methyl group of the Cp* of the cobalt complex to give [(C5Me4CH2SC5H4N)Co(S2C2B10H10)] (7). No such activation of a methyl group of the Cp* of the rhodium complex occurred, and Cp*Rh[Py(H)S](S2C2B10H10) (8) was the product.