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Chalcogenolate ligands have been known since the beginning of coordination chemistry. Thiolate chemistry is much more developed than that of the selenolate or tellurolate analogues and consequently more application‐oriented work has appeared for the former. They are important not only from the synthetic and structural point of view but also for possible applications in several areas.

In this chapter we focus on the following topics:( 1) preparation and stability of these compounds; (2) their use as ligands towards metallic centres. We separate the latter study according to: (a) main group elements, pointing out the use of alkaline and other metal complexes in the synthesis of organic compounds and transition or rare earth metal complexes, (b) transition metal complexes (excluding metalloenzymes), and (c) rare earth complexes. In these two last parts special attention is paid to the synthetic aspects because the preparation methods vary depending on the starting materials such as REH, REER, R3PE, RE‐M+ etc., structural diversity, and different coordination modes. The properties of those complexes susceptible to present or future applications are also mentioned.

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