Electrocatalytic Semihydrogenation of Alkynes with [Ni(bpy)(3)](2+)

[Image: see text] Electrifying the production of base and fine chemicals calls for the development of electrocatalytic methodologies for these transformations. We show here that the semihydrogenation of alkynes, an important transformation in organic synthesis, is electrocatalyzed at room temperature by a simple complex of earth-abundant nickel, [Ni(bpy)(3)](2+). The approach operates under mild conditions and is selective toward the semihydrogenated olefins with good to very good Z isomer stereoselectivity. (Spectro)electrochemistry supports that the electrocatalytic cycle is initiated in an atypical manner with a nickelacyclopropene complex, which upon further protonation is converted into a putative cationic Ni(II)–vinyl intermediate that produces the olefin after electron–proton uptake. This work establishes a proof of concept for homogeneous electrocatalysis applied to alkyne semihydrogenation, with opportunities to improve the yields and stereoselectivity.