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Accessing stable magnesium acyl compounds : reductive cleavage of esters by magnesium(I) dimers

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Date
09/10/2017
Author
Boutland, Aaron J.
Lamsfus, Carlos A.
Maitland, Brant
Maron, Laurent
Stasch, Andreas
Jones, Cameron
Keywords
Magnesium acyl
Magnesium(I)
Ester cleavage
Reduction
Umpolung
QD Chemistry
DAS
Metadata
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Abstract
The first examples of magnesium acyls, [(Nacnac)Mg{μ-C(Ph)O}(μ-OR)Mg(Nacnac)] (R = Me, But or Ph; Nacnac = [HC(MeCNAr)2]-; Ar = C6H2Me3-2,4,6 (MesNacnac), C6H3Et2-2,6 (DepNacnac), C6H3Pri2-2,6 (DipNacnac)), have been prepared by reductive cleavage of a series of esters using dimeric magnesium(I) reducing agents, [{(Nacnac)Mg}2]. Crystallographic studies reveal the complexes to be dimeric, being bridged by both phenyl-acyl and alkoxide/aryloxide fragments. The crystal structures, combined with results of spectroscopic and computational studies suggest that the nature of the acyl ligands within these complexes should be viewed as lying somewhere between anionic umpolung acyl and oxo-carbene. However, reactions of the acyl complexes with a variety of organic electrophiles did not provide evidence of umpolung acyl reactivity. A number of attempts to prepare alkoxide free magnesium acyls were carried out, and while these were unsuccessful, they did lead to unusual products, the crystallographic and spectroscopic details of which are discussed.
Citation
Boutland , A J , Lamsfus , C A , Maitland , B , Maron , L , Stasch , A & Jones , C 2017 , ' Accessing stable magnesium acyl compounds : reductive cleavage of esters by magnesium(I) dimers ' , Chemistry - A European Journal , vol. 23 , no. 56 , pp. 14049-14055 . https://doi.org/10.1002/chem.201703061
Publication
Chemistry - A European Journal
Status
Peer reviewed
DOI
https://doi.org/10.1002/chem.201703061
ISSN
0947-6539
Type
Journal article
Rights
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/chem.201703061
Description
C.J. and A.S. thank the Australian Research Council for financial support. C.J. also thanks the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043).
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  • University of St Andrews Research
URL
http://onlinelibrary.wiley.com/doi/10.1002/chem.201703061/full#footer-support-info
URI
http://hdl.handle.net/10023/15974

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