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Abstract Thiolates are presently a subject of great interest in the chemistry of complexes involving transition‐metal elements and soft ligands. The manifold electronic and steric capabilities offered by the monodentate ligands RS ⊖ and the bidentate chelate ligands ⊖ SRS ⊖ have been used to stabilize a broad spectrum of mononuclear, oligomeric, and polymeric complexes with new and remarkable structures and properties. Impetus has especially been provided by the synthesis of polynuclear cagelike homo‐ and heteroleptic metal–sulfur frameworks, which can often be regarded as “molecular fragments” of the structures of inorganic sulfides. Thiolates and mixed sulfide‐thiolates of the late open‐ and closed‐shell 3d metals (Fe, Co, Ni, Cu, Zn) and some of their homologues (Au, Cd, Hg), as well as of Mo, are of particular importance as model complexes for biologically important metal centers coordinated by sulfur. They have played an important role in increasing our understanding of the structure, bonding, and function of the reactive centers in ferredoxins, rubredoxins, nitrogenases, blue copper proteins, metallothioneins, and antiarthritic drugs.
Krebs et al. (Mon,) studied this question.