Ferrocene-Based Trimethylsilyl Chalcogenide Reagents for the Assembly of Functionalized Metal-Chalcogen Architectures

The ferrocene‐based trimethylsilyl chalcogenide reagents [FcC(O)OCH2CH2ESiMe3] (2, E=S, 3 E=Se, Fc=[Fe(η5‐C5H5)(η5‐C5H4)]) and [FcC(O)NHCH2CH2SSiMe3] (8b) have been synthesized. The reagents were reacted with solubilized transition‐metal acetates to yield functionalized complexes and clusters, including the spherical nanocluster [Ag14S{SCH2CH2O(O)CFc)}12(PPh3)6] (11, PPh3=triphenylphosphine). The complexes were characterized by NMR spectroscopy and X‐ray crystallography. The electrochemical behavior of the complexes was explored by cyclic voltammetry and each displayed a single quasi‐reversible redox wave with some adsorption to the electrode surface. The more, the merrier: New ferrocene‐based trimethylsilyl chalcogenide reagents have been prepared and used for the assembly of polyferrocenyl metal–chalcogen complexes and cluster frameworks, including the spherical nanocluster [Ag14S{SCH2CH2O(O)CFc}12(PPh3)6] (Fc=[Fe(η5‐C5H5)(η5‐C5H4)], PPh3=triphenylphosphine, see graphic).