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

摘要

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)I-2 (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 resultedin C-Hactivation of amethyl 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.