Do dihydroxymagnesium carboxylates form Grignard-type reagents? A theoretical investigation on decarboxylative fragmentation

Alexander Ruf, Basem Kanawati, Philippe Schmitt-Kopplin

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Dihydroxymagnesium carboxylates [(OH)2MgO2CR] were probed for decarboxylation on a theoretical level, by utilizing both Møller-Plesset perturbation theory (MP2) and density functional theory (B3LYP-DFT) computations. This study is connected to the question of whether this recently introduced, astrobiologically relevant chemical class may form Grignard-type reagent molecules. To extract trends for a broad molecular mass range, different linear alkyl chain lengths between C4 and C11 were computed. The forward energy barrier for decarboxylation reactions increases linearly as a function of the ligand’s chain length. Decarboxylation-type fragmentations of these organomagnesium compounds seem to be improbable in non-catalytic, low energetic environments. A high forward energy barrier (EMP2 > 55 kcal mol−1) towards a described transition state restricts the release of CO2. Nevertheless, we propose the release of CO2 on a theoretical level, as been revealed via an intramolecular nucleophilic attack mechanism. Once the challenging transition state for decarboxylation is overcome, a stable Mg–C bond is formed. These mechanistic insights were gained by help of natural bond orbital analysis. The Cα atom (first carbon atom in the ligand chain attached to the carboxyl group) is thought to prefer binding towards the electrophilic magnesium coordination center, rather than towards the electrophilic CO2-carbon atom. Additionally, the putatively formed Grignard-type OH-bearing product molecules possess a more polarized Mg–C bond in comparison to RMgCl species. Therefore, carbanion formation from OH-bearing Grignard-type molecules is made feasible for triggering C–C bond formation reactions. [Figure not available: see fulltext.].

Original languageEnglish
Article number106
JournalJournal of Molecular Modeling
Issue number4
StatePublished - 1 Apr 2018


  • Astrochemistry
  • DFT
  • Grignard reagent
  • MP2
  • NBO
  • Organomagnesium molecules
  • Organometallics


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