Abstract
The new β-diketimine (iPrDip) nacnacH, HC(iPrCNDip)(2) H, Dip=2,6-iPr(2) -C(6) H(3) , was converted to the magnesium(I) complex [{((iPrDip) nacnac)Mg}(2) ] and reaction with 2-adamantanone (OAd) afforded the ketone-1,2-diide complex [{((iPrDip) nacnac)Mg}(2) (μ-OAd)]. The complex contains the first stable dianion of an aliphatic ketone with an electropositive metal and shows an OAd(2-) 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.