Organotrifluoroborates have been oxidized by copper(II) salts and Dess–Martin periodinane via radical intermediates, as evidenced by TEMPO spin‐trapping experiments. This new method of radical generation is compatible with functionalization and CC bond formation through Giese‐type addition reactions (see scheme; DMSO=dimethyl sulfoxide, TEMPO=2,2,6,6‐tetramethyl‐1‐piperidinyloxyl, free radical).

No cat.s allowed: A stable and isolable tricoordinate silicon(II) hydride stabilized by a phosphine ligand was successfully synthesized and fully characterized (see structure, Si green, P yellow, N blue, C gray, H white). Interestingly, this silicon hydride adds to olefins in an unprecedented catalyst‐free hydrosilylation reaction in very mild conditions.