Splitting Molecular Oxygen en Route to a Stable Molecule Containing Diphosphorus Tetroxide

In contrast to stable phosphorus oxides such as P₄O₆ and P₄O₁₀ that possess iconic adamantane-like cage structures, highly reactive phosphorus oxides such as PO, PO₂, and P₂O_x (x = 1–5) only have been studied in the gas phase or by matrix isolation techniques. Elusive diphosphorus tetroxide, the long sought phosphorus analogue of N₂O₄, is particularly noteworthy. Computations predict that the oxo-bridged O₂POPO form of P₂O₄ is energetically more favored than the P–P bonded O₂P–PO₂ isomer. Herein, we report the experimental realization of diphosphorus tetroxidein its energetically disfavored O₂P–PO₂ formvia carbene-stabilization. The synthesis of the title compound involves the splitting of molecular oxygen by carbene-stabilized diphosphorus.