Unusual Influence of the Structures of Transition Metal Complexes on Catalytic C–S and C–Se Bond Formation Under Homogeneous and Heterogeneous Conditions

In the presence of transition metal catalysts, hydrothiolation and hydroselenation reactions, as well as bisthiolation and bisselenation reactions, have been successfully carried out with high selectivities and yields. New transition metal‐catalyzed synthetic methods have been developed for the preparation of vinyl sulfides and vinyl selenides of various types. Mechanistic study has revealed that a homogeneous catalytic system based on phosphine complexes of palladium is the best choice for carrying out stereoselective additions of disulfides and diselenides to alkynes. A heterogeneous Ni‐catalyzed reaction with a unique self‐organized nanostructured catalyst was superior for carrying out regioselective additions of thiols and selenols to alkynes.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)