Redox Convergent Synthesis and Reactivity of a Cobalt(III)‐Pentasulfido Compound.

A new mononuclear cobalt(III)‐pentasulfido compound, [(L)Co(S5)] (3) has been synthesized by using a convergent redox reaction between elemental sulfur and two new cobalt(II)‐thiolato compounds, [(L)Co(SR)] (R=Ph, 2 a; 2,6‐Me2‐C6H4, 2 b), which in turn were synthesized from a dimeric cobalt(II) complex, [(L)2Co2]2+ (1). Compound 3 features a low‐spin, diamagnetic, Co(III) center with a coordinated pentasulfido (S52−) chain and has no precedence in the literature. Compound 3 is highly stable towards reduction with a potential of −1.36 V (vs. Cp2Fe+/Cp2Fe) and gives back 1 upon chemical/electrochemical reduction. Reaction of 3 with phosphines yields back 1 and phosphine sulfides, while protonation of the coordinated S52− chain in 3 leads to the formation of 1, elemental sulfur and H2S. Finally, transfer of the coordinated S52− chain in 3 to selected organic compounds, such as MeI, PhCH2Br and PhCOCl, for the generation of organopolysulfido compounds has been demonstrated. [ABSTRACT FROM AUTHOR]