Recent Advances in the Syntheses and Catalytic Applications of Homonuclear Ru‐, Rh‐, and Ir‐Complexes of CNHC^C Cyclometalated Ligands.

In the past few decades, chemistry of cyclometalated species has gained momentum with increased applications in several areas of scientific developments. Cyclometalation reactions result in the formation of stable metallacycles through the generation of metal‐carbon covalent bonds by activating the unreactive Csp2‐H or Csp3‐H bonds. The extra stability gained by the formation of metallacycles enhances their applicability scopes especially in the area of homogeneous catalysis. In the recent research development in this area, NHC ligands (strong σ‐donor and generally, weak π‐acceptor) have been found to be one of the most suitable candidates for the intramolecular C−H activation process which leads to the cyclometalated species. The growth in the area of cyclometalation chemistry that started in the late 20th century is still continuing and in the past few decades, various examples of NHC derived transition metal‐based cyclometalated complexes came into the picture. As covering all the reported literatures in this area (includes mainly late transition metals) will exceed the limits of minireview, we restricted ourselves to the recent (2015 – May 2021) examples of the most common Ru‐, Rh‐, and Ir‐based CNHC^C cyclometalated complexes and their applications in various homogeneous catalytic conversions such as transfer hydrogenation, amidation, oxidation of alcohols, annulations, and so forth. [ABSTRACT FROM AUTHOR]