Abstract
Recently, an increasing number of metal complex catalysts have been developed to achieve the activation or transformation of substrates based on cooperation between the metal atom and its ligands. In such “cooperative catalysis,” the ligand not only is bound to the metal, where it exerts steric and electronic effects, but also functionally varies its structure during the elementary processes of the catalytic reaction. In this review article, we focus on metal–ligand cooperation involving aromatization and dearomatization of the ligand, thus introducing the newest developments and examples of homogeneous catalytic reactions.
Highlights
Current strategies in synthetic organic chemistry strongly require that chemical transformations be realized with inexpensive, available, and safe starting materials
The ligands in a metal complex catalyst were mainly expected to exhibit (1) steric effects that influenced the spatial environment around the metal and (2) electronic effects that affected the electronic character of the metal center
Sortais et al reported the Mn-catalyzed hydrogenation of ketones (Scheme 5) [50], wherein both aromatic and aliphatic ketones were reduced in the presence of Mn catalyst 8 and KOt-Bu in toluene at 130 °C under 50 bar H2 to the corresponding alcohols in good yields
Summary
Current strategies in synthetic organic chemistry strongly require that chemical transformations be realized with inexpensive, available, and safe starting materials. An increasing number of metal complex catalysts have been recently developed to achieve the activation or transformation of substrates based on cooperation between the metal atom and ligands [3,4]. In such cases, in addition to the conventional effects (steric and electronic), the ligand is bound to the metal but functions by varying its structure during the elementary processes of the catalytic reaction. There are reviews covering this subject [7,8] Another example of a complex catalyst that shows metal–ligand cooperation is based on the interconversion between a hydroxycyclopentadienyl and cyclopentadienone-type ligand.
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