Metal-sulfur centers play an important role in the activity of metalloproteins in enzymatic catalysis and the activity of metal sulfides as heterogeneous catalysts. The systematic search for M[BOND]S model compounds led to the discovery of an interesting and novel structural chemistry, which stems from the numerous coordination possibilities of sulfur ligands. The intention of this review article is to present and outline new approaches to sulfur chemistry from the organometallic point of view. Reactive cyclopentadienyl-transition metal fragments incorporate elemental sulfur to give polynuclear sulfur-rich complexes, which can contain either mono-, di- or polysulfido ligands or several such ligands in combined form. The versatile structural chemistry of the complexes formed and their reactivity towards organic, inorganic and organometallic compounds are discussed, and examples of some simple and rational procedures for their synthesis starting from cyclopentadienylcarbonyl- and cyclopentadienylhydrido-complexes are outlined. Their reactivity is manifested in numerous metal- and ligandcentered reactions. Finally the, albeit far less extensive, complex chemistry of the other chalcogens (O, Se, Te) is also considered for comparison, thus providing a more detailed survey of particular aspects of this area of chemistry.