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 (2, 4^Me, and 8–10), including the novel phosphaethynolate Grignard reagent (2^iPr). The methylmagnesium phosphaethynolate and magnesium diphosphaethynolate complexes readily activate dioxane with subsequent H-atom abstraction to form [(NHC)MgX(μ-OEt)]₂ [X = Me (3) or OCP (8 and 9)] complexes. Their reactivities increased with the Lewis acidity of the Mg²⁺ 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)₃Na(OCP) (6), which is soluble in aromatic hydrocarbons and can be independently prepared by the reaction of NHC and [Na(dioxane)₂][OCP] in toluene. Under forcing conditions (105 °C, 3 days), the magnesium diphosphaethynolate complex (NHC)₃Mg(OCP)₂ (10) decomposes to a mixture of organophosphorus complexes, among which a thermal decarbonylation product [(NHC)₂P^I][OCP] (11) was isolated.