Carbonyl group and carbon dioxide activation by rare-earth-metal complexes

The rare-earth elements (Ln = Sc, Y, La-Lu) are widely used in stoichiometric and catalytic carbonyl group transformations. Sufficient availability, non-toxicity, high oxophilicity, tunable ion size/Lewis acidity and enhanced ligand exchangeability have been major driving factors for their successful implementation. Routinely employed reagents for stoichiometric carbonyl group transformations are divalent ytterbium and samarium compounds (e.g., ketone reduction), bimetallic CeCl3/LiR (C-C coupling), or ceric ammonium nitrate CAN (cyclic ketone oxidation). Rare-earth-metal triflates, and in particular Sc(OTf)3, are prominent examples of Lewis acid catalysts for versatile use in organic synthesis (e.g., Aldol and Michael reactions). Moreover, Ln(ii) and Ln(iii) complexes efficiently catalyze the (co)polymerization of carbonyl group-containing monomers including lactones, lactides, acrylates, and carbon dioxide. Featuring the most notorious greenhouse gas, CO2 is currently assessed as a cheap, abundant, and non-toxic C1 building block. Ln(iii) complexes are not only capable of efficient CO2 capture via reversible insertion but also of CO2 activation for catalytic conversions (copolymerization/cycloaddition with epoxides). This perspective focuses on structurally elucidated Ln complexes resulting from ketone or carbonyl derivative activation/insertion as well as carbon dioxide insertion products. The respective compounds will be sorted by structural motifs and, if applicable, details on reactivity and feasibility of catalytic reactions are presented. The article is subdivided in three parts: (i) donor and insertion products of ketones and aldehydes, (ii) redox-enhanced activation of carbonyl derivatives, and (iii) CO2 insertion/redox products and homogeneous catalytic conversion.