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

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.

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hlca202100042-s1-si_birh_rhrh_mepy_v3.pdf (Supplementary material), 4MB
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hlca202100042-s1-si_birh_rhrh_mepy_v3.pdf
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 Creators:
Löffler, Lorenz E.1, Author              
Buchsteiner, Michael1, Author              
Collins, Lee R.1, Author              
Caló, Fabio P.1, Author              
Singha, Santanu1, Author              
Fürstner, Alois1, Author              
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1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              

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Free keywords: bismuth: carbenes; cyclopropanation; heterobimetallic complexes; rhodium
 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.

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Language(s): eng - English
 Dates: 2021-03-172021-04-202021-06-01
 Publication Status: Published online
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/hlca.202100042
 Degree: -

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Title: Helvetica Chimica Acta
  Abbreviation : Helv. Chim. Acta
Source Genre: Journal
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Publ. Info: Zürich : Verlag Helvetica Chimica Acta AG
Pages: - Volume / Issue: 104 (6) Sequence Number: e2100042 Start / End Page: - Identifier: ISSN: 0018-019X
CoNE: https://pure.mpg.de/cone/journals/resource/954925403620