Insights into the mechanism of the unusual trans‐hydrogenation of internal alkynes catalyzed by {Cp*Ru} complexes were gained by para‐hydrogen (p‐H₂) induced polarization (PHIP) transfer NMR spectroscopy. It was found that the productive trans‐reduction competes with a pathway in which both H atoms of H₂ are delivered to a single alkyne C atom of the substrate while the second alkyne C atom is converted into a metal carbene. This “geminal hydrogenation” mode seems unprecedented; it was independently confirmed by the isolation and structural characterization of a ruthenium carbene complex stabilized by secondary inter‐ligand interactions. A detailed DFT study shows that the trans alkene and the carbene complex originate from a common metallacyclopropene intermediate. Furthermore, the computational analysis and the PHIP NMR data concur in that the metal carbene is the major gateway to olefin isomerization and over‐reduction, which frequently interfere with regular alkyne trans‐hydrogenation.

Insights into the mechanism of the unusual trans‐hydrogenation of internal alkynes catalyzed by {Cp*Ru} complexes were gained by para‐hydrogen (p‐H₂) induced polarization (PHIP) transfer NMR spectroscopy. It was found that the productive trans‐reduction competes with a pathway in which both H atoms of H₂ are delivered to a single alkyne C atom of the substrate while the second alkyne C atom is converted into a metal carbene. This “geminal hydrogenation” mode seems unprecedented; it was independently confirmed by the isolation and structural characterization of a ruthenium carbene complex stabilized by secondary inter‐ligand interactions. A detailed DFT study shows that the trans alkene and the carbene complex originate from a common metallacyclopropene intermediate. Furthermore, the computational analysis and the PHIP NMR data concur in that the metal carbene is the major gateway to olefin isomerization and over‐reduction, which frequently interfere with regular alkyne trans‐hydrogenation.