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Jacobsen's catalyst for hydrolytic kinetic resolution: structure elucidation of paramagnetic Co(III) salen complexes
Sebastian Kemper1, Peter Hrobárik, Martin Kaupp
1Department für Chemie, Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany.
Abstract:
NMR investigation of chiral Co(III) salen catalysts, important for enantioselective hydrolytic kinetic resolution (HKR), revealed the presence of a paramagnetic high-spin Co(III) species, which is in solvent- and temperature-dependent equilibrium with the known diamagnetic low-spin Co(III) complex. Combined with quantum chemical DFT calculations, the para- and diamagnetic chemical shifts were used to study the salen ligand conformation of the para- and diamagnetic complexes, resulting in a mechanistic proposal for the enantioselective step in catalysis.
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