Heteroatom-Free Arene-Cobalt and Arene-Iron Catalysts for Hydrogenations
M. Sc. Dominik Gärtner
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorDr. Alice Welther
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorDr. Babak Rezaei Rad
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Robert Wolf
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)Search for more papers by this authorCorresponding Author
Prof. Dr. Axel Jacobi von Wangelin
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)Search for more papers by this authorM. Sc. Dominik Gärtner
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorDr. Alice Welther
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorDr. Babak Rezaei Rad
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Robert Wolf
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)Search for more papers by this authorCorresponding Author
Prof. Dr. Axel Jacobi von Wangelin
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)
Fakultät für Chemie, Universität Regensburg, Universitätsstrasse 31, 93040 Regensburg (Germany)Search for more papers by this authorGraphical Abstract
Especially high selectivities were observed in the hydrogenation of various alkenes, ketones, and imines with bis(anthracene)cobaltate(−I) [K(dme)2{Co(C14H10)2}] under mild conditions (1–5 mol % cat., 1–10 bar H2, 20–60 °C). Mechanistic studies indicate the operation in alkene hydrogenations of a homogeneous catalyst formed by initial ligand exchange and stabilized by the coordination of π-acidic alkenes or arenes.
Abstract
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 π 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 π 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.
Supporting Information
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