As the generated silylated Grignard intermediates seem to be too unreactive for further silylation, to give the targeted [FeC10DMS10], organolithium compounds were used instead. Herein the lithium is introduced by lithium-halogen exchange with t BuLi and FeC10Br10 followed by addition of DMSCl. The introduction of lithium in ortho-position to bromine can cause a subsequent elimination of lithium bromide, which is known for several aryls followed by aryne formation and decomposition. Therefore, lithiation agent and electrophile were added at -100°C. The stability of the lithiated species varies depending on the solvents. While in n-pentane the compounds only decompose slowly at room temperature, which can be explained by the low solubility in alkanes, in THF and Et2O decomposition was observed above ca. -80°C. The silylation itself was mainly observed between ca. -80°C and room temperature in THF and in n-pentane between -50°C to room temperature indicating that the silylation proceeds faster in THF. However, in Et2O the lithiated intermediates decompose before the silylation process starts. The mass spectra of the reactions in THF and n-pentane still revealed incomplete substitution as after the first lithiation attempt with up to 80 equivalents t BuLi in both cases brominated species were still visible at m/z = 672. improved conversion is achieved by multiple metalation cycles. Here, the choice of the solvent becomes more important after multiple lithiation and silylation iterations. While after four iterations in n-pentane brominated species are still visible in the mass spectra, in THF three iterations are sufficient to transform all brominated compounds. However, the formation of side products at m/z = 606.1510 (FeC25H54Si7), m/z = 680.2075 (FeC28H64Si8) and m/zfound = 738.2315 (FeC30H70Si9) is observed (Figure , bottom). As n-pentane still offers sufficient reaction speed it was chosen to be the most suitable solvent for the first lithiation and later changed to THF to reduce side reactions. Nevertheless, via this approach we were able to isolate the desired [FeC10(DMS)10] ( ) in milligram amounts.