Abstract
[(NHC)(cymene)RuCl2] (NHC=N‐heterocyclic carbene) complexes instigate a light‐driven gem‐hydrogenation of internal alkynes with concomitant formation of discrete Grubbs‐type ruthenium carbene species. This unorthodox reactivity mode is harnessed in the form of a “hydrogenative metathesis” reaction, which converts an enyne substrate into a cyclic alkene. The intervention of ruthenium carbenes formed in the actual gem‐hydrogenation step was proven by the isolation and crystallographic characterization of a rather unusual representative of this series carrying an unconfined alkyl group on a disubstituted carbene center.
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