Heteroatom-Free Arene-Cobalt and Arene-Iron Catalysts for Hydrogenations

75 years after the discovery of hydroformylation, cobalt catalysts are now undergoing a renaissance in hydrogenation reactions. We have evaluated arene metalates in which the low-valent metal species is-conceptually different from heteroatom-based ligands-stabilized by pi coordination to hydrocarbons. Potassium bis(anthracene)cobaltate 1 and -ferrate 2 can be viewed as synthetic precursors of quasi-naked anionic metal species; their aggregation is effectively impeded by (labile) coordination to the various p acceptors present in the hydrogenation reactions of unsaturated molecules (alkenes, arenes, carbonyl compounds). Kinetic studies, NMR spectroscopy, and poisoning studies of alkene hydrogenations support the formation of a homogeneous catalyst derived from 1 which is stabilized by the coordination of alkenes. This catalyst concept complements the use of complexes with heteroatom donor ligands for reductive processes.