Tuning the Electron Acceptability of the [Mo6S8] Cluster Core by Decorating It with Methyl Groups on the Face‐Bridging µ3‐Sulfides.

Methylation of the molybdenum sulfide cluster unit [Mo₆S₈(PEt₃)₆] (1) with CH₃OTf resulted in the formation of mono‐ and dimethylated cluster units, [Mo₆S_8–x(SCH₃)_x(PEt₃)₆]OTf·yCH₂Cl₂ {[2]OTf·0.5CH₂Cl₂ (x = 1, y = 0.5) and [3]OTf·CH₂Cl₂ (x = 2, y = 1)}. Structural and electrochemical investigations revealed that the methylation of the µ₃‐S ligand(s) induced a characteristic structural distortion of the [Mo₆S₈] cluster core and enhanced its ability to accept multiple electrons. [ABSTRACT FROM AUTHOR]