Metal complexes of backbone-halogenated imidazol-2-ylidenes.

In this manuscript, literature reports on mono- and di-halogen (F, Cl, Br, and I) substituted at positions 4 or/and 4,5 imidazol-2-ylidene (NHC) metal complexes are discussed: particularly, their structural diversity with various metals (groups 6-13), important physicochemical properties, catalytic and medicinal/biological applications are reviewed. To our knowledge, there are no literature reports on group 4 and 5 metal complexes with this type of NHC ligands. Halogenated imidazol-2-ylidene metal complexes deserve special attention because halogens are the classic electron donating groups (mesomerically) in conjugated aromatic/heteroaromatic ring systems, but electron withdrawing inductively. However, they exhibit a significant electron withdrawing inductive effect, thus providing unique electronic properties. This is important for fine tuning of σ-donor abilities of the "carbenic" carbon of imidazol-2-ylidenes, which directly affect catalytic performance of their metal complexes. Other applications, advantages, and disadvantages of halogenated vs. unsubstituted imidazol-2-ylidene metal complexes are critically analyzed and summarized in this review.