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Published on: December 29, 2016
Redox Convergent Synthesis and Reactivity of a Cobalt(III)-Pentasulfido Compound
1School of Chemical Sciences Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road Jadavpur, Kolkata, 700032, West Bengal, India.
Abstract:
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 -C6 H4 , 2 b), which in turn were synthesized from a dimeric cobalt(II) complex, [(L)2 Co2 ]2+ (1). Compound 3 features a low-spin, diamagnetic, Co(III) center with a coordinated pentasulfido (S5 2- ) chain and has no precedence in the literature. Compound 3 is highly stable towards reduction with a potential of -1.36 V (vs. Cp2 Fe+ /Cp2 Fe) and gives back 1 upon chemical/electrochemical reduction. Reaction of 3 with phosphines yields back 1 and phosphine sulfides, while protonation of the coordinated S5 2- chain in 3 leads to the formation of 1, elemental sulfur and H2 S. Finally, transfer of the coordinated S5 2- chain in 3 to selected organic compounds, such as MeI, PhCH2 Br and PhCOCl, for the generation of organopolysulfido compounds has been demonstrated.
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