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Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge
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dc.contributor.author | Burnett, Stuart | |
dc.contributor.author | Bourne, Connor | |
dc.contributor.author | Slawin, Alexandra M. Z. | |
dc.contributor.author | van Mourik, Tanja | |
dc.contributor.author | Stasch, Andreas | |
dc.date.accessioned | 2022-07-11T16:30:02Z | |
dc.date.available | 2022-07-11T16:30:02Z | |
dc.date.issued | 2022-08-16 | |
dc.identifier | 280273433 | |
dc.identifier | 68176f75-0c72-46ed-ad5e-68d5f6270e33 | |
dc.identifier | 85133723787 | |
dc.identifier | 000822834100001 | |
dc.identifier.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 | en |
dc.identifier.issn | 1433-7851 | |
dc.identifier.other | RIS: urn:CFF68EAEDC986941ADD708089EA1D95F | |
dc.identifier.other | ORCID: /0000-0002-9527-6418/work/115941504 | |
dc.identifier.other | ORCID: /0000-0001-7683-3293/work/115941684 | |
dc.identifier.other | ORCID: /0000-0002-7407-8287/work/115941998 | |
dc.identifier.uri | https://hdl.handle.net/10023/25650 | |
dc.description | We thank the University of St Andrews and the EPSRC doctoral training grant (EP/N509759/1) for support. | en |
dc.description.abstract | 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. | |
dc.format.extent | 10 | |
dc.format.extent | 1470427 | |
dc.language.iso | eng | |
dc.relation.ispartof | Angewandte Chemie International Edition | en |
dc.subject | Dianions | en |
dc.subject | Low oxidation states | en |
dc.subject | Magnesium | en |
dc.subject | Reductions | en |
dc.subject | Umpolung | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Umpolung of an aliphatic ketone to a magnesium ketone-1,2-diide complex with vicinal dianionic charge | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.contributor.institution | University of St Andrews. Centre for Research into Equality, Diversity & Inclusion | en |
dc.identifier.doi | 10.1002/anie.202204472 | |
dc.description.status | Peer reviewed | en |
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