Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge
Date
16/08/2022Metadata
Show full item recordAbstract
The new ß-diketimine iPrDipnacnacH, HC(iPrCNDip)2H, Dip=2,6- iPr2-C6H3 , was converted to the magnesium(I) complex [{(iPrDipnacnac)Mg}2] and reaction with 2-adamantanone (OAd) afforded the ketone-1,2-diide complex [{(iPrDipnacnac)Mg}2(µ -OAd)]. The complex contains the first stable dianion of an aliphatic ketone with an electropositive metal and shows an OAd2- unit with long C-O bond and pyramidal carbon centre. DFT studies reveal an anionic charge on both neighbouring C and O atoms. Reductions of aliphatic ketones with magnesium(I) complexes show that these likely proceed via highly reactive dianions and afforded a 1:1 mixture of an alkoxide and an enolate when an enolisable ketone was used, and rapid CH activations reactions, e.g., of stabilising ligand moieties, when non-enolisable ketones were employed.
Citation
Burnett , S , Bourne , C , Slawin , A M Z , van Mourik , T & Stasch , A 2022 , ' Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge ' , Angewandte Chemie International Edition , vol. 61 , no. 34 , e202204472 . https://doi.org/10.1002/anie.202204472
Publication
Angewandte Chemie International Edition
Status
Peer reviewed
ISSN
1433-7851Type
Journal article
Description
We thank the University of St Andrews and the EPSRC doctoral training grant (EP/N509759/1) for support.Collections
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