AbstractThe cover picture shows the impact of the phosphane ligand on solid metal nanoparticles, which initiates transformation of the metal species into a high‐performance catalyst. The evolution of the transition‐metal complexes was monitored by NMR spectroscopy, and the active form of the catalyst was detected in the 2D HMQC spectrum. A novel synthetic procedure to access cyclic vinyl chalcogenides was developed by utilizing an in situ designed catalyst in an E–E bond addition reaction to acetylenes (E = S, Se). Details are discussed in the article by V. P. Ananikov, I. P. Beletskaya et al. on p. 1149 ff.