Abstract
AbstractThe new β‐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.
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