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Journal Article

[Rh2(MEPY)4] and [BiRh(MEPY)4]: Convenient Syntheses and Computational Analysis of Strikingly Dissimilar Siblings

MPS-Authors
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Löffler,  Lorenz E.
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Buchsteiner,  Michael
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Collins,  Lee R.
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Caló,  Fabio P.
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Singha,  Santanu
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Supplementary Material (public)

hlca202100042-s1-si_birh_rhrh_mepy_v3.pdf
(Supplementary material), 4MB

Citation

Löffler, L. E., Buchsteiner, M., Collins, L. R., Caló, F. P., Singha, S., & Fürstner, A. (2021). [Rh2(MEPY)4] and [BiRh(MEPY)4]: Convenient Syntheses and Computational Analysis of Strikingly Dissimilar Siblings. Helvetica Chimica Acta, 104(6): e2100042. doi:10.1002/hlca.202100042.


Cite as: https://hdl.handle.net/21.11116/0000-0008-C3C0-2
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. Likewise, 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.