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  1. Redox-inert metal cations change the reaction between thiolate anions and elemental sulfur. Spectroscopic and electrochemical data show that metal–sulfur covalency determines the favorability of sulfur catenation vs. sulfur reduction. 
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  2. The interactions between transition metals and sulfur have long been studied for potential applications in catalysis and energy storage and due to the relevance of these motifs in biological and geological systems. Complexes with sulfur-containing ligands can undergo redox transformations centered on sulfur as well as at the metal. Sulfur also readily catenates with other sulfur centers to form polysulfur motifs. Here, the synthesis and structures of notable examples of metal complexes with sulfur-containing ligands (sulfido, polysulfido, and polysulfanido) are described. Aspects of sulfur-centered redox, including spectroscopic and structural considerations, and future research opportunities are highlighted. 
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