Metal-cation-induced shifts in thiolate redox and reduced sulfur speciation.

Sulfur-containing anions (e.g. thiolates, polysulfides) readily exchange in solution, making control over their solution speciation and distribution challenging. Here, we demonstrate that different redox-inactive alkali, alkaline earth, and transition metals (Li+, Na+, K+, Mg2+, Ca2+, Zn2+, and Cd2+) shift the equilibria of sulfur catenation or sulfur reduction/oxidation between thiolate, polysulfanide, and polysulfide anions in acetonitrile solution. The thermodynamic factors that govern these equilibria are examined by identification of intermediate metal thiolate and metal polysulfide species using a combination of NMR spectroscopy, electronic absorption spectroscopy, and mass spectrometry. Electrochemical measurements demonstrate that the metal cation of the electrolyte modulates both sulfur reduction and thiolate oxidation potentials. DFT calculations suggest that the changes in equilibria are driven by stronger covalent interactions between polysulfide anions and more highly charged cations.

Cluster self-assembly and anion binding by metal complexes of non-innocent thiazolidinyl-thiolate ligands.

ZnII and FeII chloride complexes of a di(methylthiazolidinyl)pyridine ligand were deprotonated to form the corresponding thiolate complexes supported by redox-active iminopyridine moieties. The thiolate donor groups are nucleophilic and reactive toward oxidants, electrophiles, and protons, while the pendant thiazolidine rings are available for hydrogen bonding. Anion exchange with the weakly-coordinating triflate anion resulted in self-assembly of the iminopyridine complexes to form a trimeric [M3S3] cluster. Hydrogen bonding closely associates anions with this trimetallic core.