Synthesis, Characterization, and Metal Complexation of Unsymmetrical 1,1‘-Bis(organylthiolato)ferrocenes

A series of new unsymmetrical 1,1‘-disubstituted ferrocenediyl ligands featuring thioether
substituents (SR, SR‘ where R ≠ R‘:  Me, Ph, tBu) have been conveniently synthesized via
cleavage of ferrocenylsulfanes. The ligands display a range of coordination chemisty,
exemplified by reaction with Pt, Pd, and W metal centers, and structural characterization
indicates the bidentate, chelating nature of the ligands. Electrochemical studies show that
the diferrocenyldisulfanes exhibit two separated one-electron oxidations where the mixed-valent monocations belong to the partially delocalized Robin-Day Class II, while for the
metallocenophanes, chemical reversibility is noted along with some decomposition over time.