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The pentachloroferrocenes [C5Cl5]Fe[C5H4X] (X = H, Br, SMe) react with LiTMP and MeSSMe to form mixtures of compounds, that contain besides the expected products of deprotonation also one or more complexes with a [C5Cl4(SMe)] ligand. This latter observation makes the otherwise rarely observed occurrence of “halogen dance reactions” in chloroaromatics very probable. 1,2,3‐Trichloroferrocene yields with BuLi and MeSSMe products of both halogen‐metal‐exchange and of deprotonation. Additionally, in all examined systems, the observation of some highly‐substituted complexes with eight or more substituents hints to the involvement of cyclopentadienyl exchange reactions, which has also rarely been observed under such mild conditions. The molecular structures of [C5Cl4(SMe)]Fe[C5H3BrX] (X = SMe or SOMe), [C5Cl4(SMe)]Fe[C5H2Cl(SMe)2], [C5Cl2(SMe)3]2Fe, and [C5HCl3(SMe)]2Fe have been determined by X‐ray diffraction.

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