A Thermally Stable Magnesium Phosphaethynolate Grignard Complex.

The 2-phosphaethynolate (OCP) anion has found versatile applications across the periodic table but remains underexplored in group 2 chemistry due to challenges in isolating thermally stable complexes. By rationally modifying their coordination environments using 1,3-dialkyl-substituted N-heterocyclic carbenes (NHCs), we have now isolated and characterized thermally stable, structurally diverse, and hydrocarbon soluble magnesium phosphaethynolate complexes (, , and ), including the novel phosphaethynolate Grignard reagent (). The methylmagnesium phosphaethynolate and magnesium diphosphaethynolate complexes readily activate dioxane with subsequent H-atom abstraction to form [(NHC)MgX(μ-OEt)] [X = Me () or OCP ( and )] complexes. Their reactivities increased with the Lewis acidity of the Mg cation and may be attenuated by Lewis base saturation or a slight increase in carbene sterics. Solvent effects were also investigated and led to the surreptitious isolation of an ether-free sodium phosphaethynolate (NHC)Na(OCP) (), which is soluble in aromatic hydrocarbons and can be independently prepared by the reaction of NHC and [Na(dioxane)][OCP] in toluene. Under forcing conditions (105 °C, 3 days), the magnesium diphosphaethynolate complex (NHC)Mg(OCP) () decomposes to a mixture of organophosphorus complexes, among which a thermal decarbonylation product [(NHC)P][OCP] () was isolated.