[Rh2(MEPY)4] and [BiRh(MEPY)4]: Convenient Syntheses and Computational Analysis of Strikingly Dissimilar Siblings |
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| Authors: | Lorenz E Löffler Michael Buchsteiner Lee R Collins Fabio P Caló Santanu Singha Alois Fürstner |
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| Institution: | 1. Max-Planck-Institut für Kohlenforschung, DE-45470 Mülheim/Ruhr, Germany
These authors contributed equally.;2. Max-Planck-Institut für Kohlenforschung, DE-45470 Mülheim/Ruhr, Germany |
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| Abstract: | Rh2(MEPY)4] is a versatile catalyst for asymmetric synthesis but its preparation requires purification by chromatography on surface-modified silica. A higher yielding procedure based on a more convenient work-up is presented herein. Moreover, a much improved method for the preparation of BiRh(OTfa)4] is described, which makes this heterobimetallic complex readily available. Subsequent exchange of the trifluoroacetate ligands opens access to a so far underappreciated family of (chiral) paddlewheel complexes. While BiRh] complexes comprising four carboxylate ligands are highly adequate for intermolecular asymmetric cyclopropanation reactions, BiRh(MEPY)4] as the heterobimetallic cousin of Rh2(MEPY)4] was found to be surprisingly unreactive; DFT calculations uncover the reasons for this inertia. |
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| Keywords: | bismuth carbenes cyclopropanation heterobimetallic complexes rhodium |
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