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- W3187237796 abstract "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, 4Me, and 8–10), including the novel phosphaethynolate Grignard reagent (2iPr). 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)2PI][OCP] (11) was isolated." @default.
- W3187237796 created "2021-08-16" @default.
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- W3187237796 date "2021-08-04" @default.
- W3187237796 modified "2023-10-18" @default.
- W3187237796 title "A Thermally Stable Magnesium Phosphaethynolate Grignard Complex" @default.
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- W3187237796 doi "https://doi.org/10.1021/acs.inorgchem.1c01700" @default.
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