The random nonracemic formation of the platinum(IV) polysulfide tris(chelate) anionic complex (NH4)2[Pt(S5)3]·2H2O, previously believed to be due to a crystallization‐induced asymmetric transformation of the reaction product, under scrutiny turned out to be a new type of autocatalytic asymmetric synthesis. The synthesis is driven by simultaneous crystallization of the product as an enantiomorphous conglomerate. In particular, the preparation becomes chemo‐ and stereoselective when carried out with continuous vigorous stirring in the presence of seeds of the desired nonracemic ultimate reaction product, i.e. an autocatalyst. However, structural characterization of the randomly obtained products by means of XRD, 195Pt NMR, and ESI‐MS measurements as well as X‐ray single‐crystal analyses, reveals the significant complexity of the reaction. Several tris(polysulfide) congeners and their stereoisomers are usually obtained, and they may even cocrystallize. All these characteristics point to the kinetic control of these autocatalytic asymmetric preparations under the applied nontrivial reaction conditions. Consequently, the composition and handedness of the products can to a large extent be controlled by seeding the reaction mixture with a small previously obtained solid sample, which contributes to the synthesis as an autocatalyst.

The cover picture shows an eruption of a volcano, which symbolically corresponds to the role of the volcanic “iron–sulfur world” and the Wächtershäuser model in the chemoautotrophic hypothesis of the origin of life, in which polysulfide species play an important role. Further details on polysulfide moieties that appear to easily adopt chiral arrangements in platinum complexes can be found in the article by W. K. Rybak et al. on p. 3675 ff. The foreground of the picture shows a figurative representation of the conglomerate crystallization‐induced asymmetric synthesis that is operating autocatalytically without any chiral auxiliary reagents. The asymmetric synthesis is triggered by exploiting seeds of the enantiomeric product and by applying vigorous stirring of the reaction mixture.