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[Rh 2 (MEPY) 4 ] and [BiRh(MEPY) 4 ]: Convenient Syntheses and Computational Analysis of Strikingly Dissimilar Siblings
Author(s) -
Löffler Lorenz E.,
Buchsteiner Michael,
Collins Lee R.,
Caló Fabio P.,
Singha Santanu,
Fürstner Alois
Publication year - 2021
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.202100042
Subject(s) - chemistry , intermolecular force , carboxylate , cyclopropanation , crystallography , catalysis , combinatorial chemistry , stereochemistry , computational chemistry , organic chemistry , molecule
[Rh 2 (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 [Rh 2 (MEPY) 4 ] was found to be surprisingly unreactive; DFT calculations uncover the reasons for this inertia.