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

摘要

In contrast to stable phosphorus oxides such as P_4O_6 and P_4O_(10) that possess iconic adamantane-like cage structures, highly reactive phosphorus oxides such as PO, PO_2, and P_2O_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 N_2O_4, is particularly noteworthy. Computa-tions predict that the oxo-bridged O_2POPO form of P_2O_4 is energetically more favored than the P-P bonded O_2P- PO_2 isomer. Herein, we report the experimental realization of diphosphorus tetroxide-in its energetically disfavored O_2P-PO_2 form-via carbene-stabilization. The synthesis of the title compound involves the splitting of molecular oxygen by carbene-stabilized diphosphorus.