Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-Defined Manganese(II) Complex

Herein we report unprecedented manganese-catalyzed semihydrogenation of internal alkynes to (<i>Z</i>)-alkenes using ammonia borane as a hydrogen donor. The reaction is catalyzed by a pincer complex of the earth-abundant manganese­(II) salt in the absence of any additives, base, or superhydride. The ammonia borane smoothly reduces the manganese precatalyst [Mn­(II)–PNP]­[Cl]₂ to the catalytically active species [Mn­(I)–PNP]–hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational density functional theory (DFT) analysis studies of the reaction mechanism rationalize the origin of stereoselectivity toward formation of (<i>Z</i>)-alkenes