NHC–Ru complexes—Friendly catalytic tools for manifold chemical transformations

N-Heterocyclic carbenes are now commonly encountered in organometallic and inorganic coordination chemistry. The increasing attention they enjoy is due to their ability to act as ancillary ligands in a growing number of transition metal catalysts or even to play the role of nucleophilic reagents and catalysts in diverse organic transformations. As a fine addition to the NHC–Ru–alkylidenes, popular for their tremendous success in metathesis chemistry, an array of robust and stable Ru–NHCs has proven their utility in non-metathetical reactions. The present review surveys different classes of Ru–NHCs and their applications as efficient catalysts (or precatalysts) in several types of fundamental organic processes e.g. hydrogenation, hydrogen transfer, isomerization, cycloisomerization, cyclopropanation, hydrosilylation, allylation and deallylation, enol-ester synthesis, heterocycle synthesis, C–C alkyne coupling, Kharasch addition and ATRP. A special section is devoted to tandem processes some of which include concurrent or sequential metathesis steps. Relevant mechanistic and stereochemical aspects related to NHC–Ru catalysis will be highlighted.