Abstract Several capto-dative olefins containing the phenylselenenyl group have been obtained via selenenyl halide addition to acrylic derivatives followed by halide elimination. Some of the olefins efficiently trap the radicals formed from azobisisobutyronitrile (AIBN) and methyl azobisisobutyrate (MAIB) to form intermediate bridged dehydrodimers, which spontaneously lose diphenyldiselenide to produce new highly functionalised ...