Catalysis of the Nitroso–Diels–Alder cycloaddition reaction between CH[formula omitted]N=O and cis-1,3-butadiene by pnictogen bonding, a theoretical study

Abstract

Density functional theory calculations at the M06-2X/aug-cc-pVTZ level of theory have been used to examine the Nitroso–Diels–Alder (N–D–A) cycloaddition reaction between the CH3N=O and cis-1,3-butadiene in the presence of PO2X (X=F, Cl, OH) as a catalyst. The effect of the above PO2X compounds on the activation energy of the N-D-A reaction, has been studied here. In the first stage, the energies of two different bonding interactions, via P⋯N versus P⋯O binding, between the PO2X and CH3N=O molecules were calculated. The results showed that the largest values of the interaction energy between the above molecules belong to the PO2F, when connects to the nitrogen atom of the CH3N=O. Also, calculations showed that all the above PO2X compounds, decrease the activation energies of N–D–A reaction studied here via both P⋯N and P⋯O interactions. However, the largest effect on activation energies of the reaction belongs to the PO2F catalyst when acts via P⋯N bonding. The activation strain model (ASM) was used to analyze the influence of the PO2X catalyst on the studied reaction. The quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis were performed to understand the nature of forming interactions at the TS structures. The results of this study showed that the PO2X (X=F, Cl, OH) compounds may be suggested as efficient catalysts for N–D–A reactions.