Computational Studies of Open-Shell Phosphorus Oxyacids. Cheletropic Reaction of PO₂ with H₂

Cramer, C. J.; Famini, G. R.
Chem. Phys. Lett. 1990, 169, 405.

Correlated, spin-unrestricted, electronic structure calculations have been performed for intermediates in the cheletropic reaction of phosphorus dioxide and hydrogen. The reaction involves a change of electronic state and has the high barrier expected for such a symmetry-forbidden, thermal process. The activation energy required by the ground state reactants is between 63 and 82 kcal/mole. However, the reaction of hydrogen with ²Pi_u PO₂ is predicted to have no barrier.