Fluorine-containing ruthenium-based olefin metathesis catalysts

The review summarizes literature data on the methods for the introduction of fluorine atoms and fluoralkyl groups into different ligands to construct metathesis-active ruthenium carbene complexes. It also analyzes the influence of fluorinated ligands on the catalytic activity of the complexes. The choice, structure and positions of fluorinated substituents in NHC ligands are generally dictated by the desire to increase the electrophilicity of the ruthenium atom due to the electron-withdrawing effect of fluorine atoms and fluoroalkyl groups, resulting, as a rule, in an increase in the activity of the ruthenium complex. In catalysts with unsymmetrical fluorine-containing NHC ligands, there is a possibility of additional Ru-F coordination, making the complexes much more stable and, consequently, more active. The presence of fluorine in chelating alkylidene ligands provides an increase in the catalyst initiation rate due to a weakening of the ruthenium - heteroatom bond. Besides, the introduction of polyfluoroalkyl groups into ligands solves the problem of catalyst recovery using fluorous biphasic systems for reuse.