Protonated methyl nitrite. A theoretical investigation on the structure and stability of (MeO-NO)H⁺ and the proton affinity of RO-NO (R = H, Me)
Authors: Aschi, Massimiliano^a; Grandinetti, Felice
Affiliations: a. Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Università di Roma ‘La Sapienza’, P.le A. Moro, 5, 00185 Rome, Italy

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Abstract
Ab initio calculations have been performed on the structure and stability of (MeO-NO)H⁺ and the proton affinity (PA) of RO-NO (R = H, Me). At the MP4/6-311G^**/ /MP2(FULL)/6-31G^* level of theory, the ion-dipole adduct MeOH-NO⁺ 1 is by far the most stable protomer. At the G2 level, the dissociation enthalpy into MeOH and NO⁺ is computed as 25.3 kcal mol^-1 and the PAs of MeO-NO and HO-NO amount to 187 and 188 kcal mol^-1, respectively. This finding marks a departure from the expected order and parallels the anomalous trend recently ascertained in the PAs of the strictly related RO-NO₂ (R = H, Me).

Publisher: Elsevier Science