The hydrogen-atom transfer from methoxy radical to nitric
oxide,
leading to the formation of formaldehyde and nitroxyl, represents
a secondary reaction of photodissociation of methyl nitrite, which
is used as rocket fuel. In this study, we explored the potential energy
profile of the hydrogen-atom transfer using the electronic structure
calculations at the DLPNO-CCSD(T)/aug-cc-pVTZ level of theory for
two isomeric forms (cis and trans) of the pre-reaction complex. The cis-oriented
pre-reaction complex has a weak elongated OO bond, which gets
further elongated in the hydrogen transfer transition state. This
OO bond stabilizes the pre-reaction complex by 32.9 kJ/mol.
The OO-induced stabilization is even greater for the transition
state (48.2 kJ/mol), which was unexpected because of the larger OO
distance in the transition state structure. To address this paradox,
we performed the electronic structure analysis of the reaction participants
using the valence bond (VB) theory, natural resonance theory, topological
analysis of the electron density and its derivatives, and analysis
of the electron localization function distribution. This combined
analysis led to the conclusion that the cis-transition
state for hydrogen transfer, instead of being directly stabilized
by the OO interaction, gained substantial stabilization from
the in-plane five-center six-electron aromaticity.