Switchable Ni-catalyzed bis-thiolation of acetylene with aryl disulfides as an access to functionalized alkenes and 1,3-dienes

•The first example of selective nickel-catalyzed disulphide addition to acetylene is reported.•Synthesis of (Z)-1,2-bis(arylthio)ethenes and (Z,Z)-1,4-bis(arylthio)butadienes-1,3 was carried out.•Utilization of particular ligand (PPh3 or PPhCy2) provides desired product.•Detailed study of reaction mechanism is provided including electron microscopy video.•Liquid-phase SEM study suggested ligand-mediated leaching from Ni-containing species as a key step of catalyst formation.