Protonated heterocyclic derivatives of cyclopropane and cyclopropanone: classical species, alternate sites, and ring fragmentation

Abstract

A computational study has been performed for protonated oxygen-or nitrogen-containing heterocyclic derivatives of cyclopropane and cyclopropanone. We have searched for the most stable conformations of the protonated species using density functional theory with the B3LYP functional and the 6-31G(2df,p) basis set. More accurate enthalpy values were obtained from G4 calculations. Proton affinities and gas-phase basicities were accordingly derived.Résumé : Nous avons réalisé une étude de modélisation sur des dérivés hétérocycliques protonés du cyclopropane ou de la cyclopropanone contenant un atome d'oxygène ou d'azote. Nous avons recherché les conformations les plus stables au moyen de la théorie de la fonctionnelle de la densité, en utilisant la fonctionnelle B3LYP et la base 6-31G(2df,p). La meilleure exactitude des valeurs d'enthalpie a été obtenue grâce aux calculs selon le modèle G4. De ces résultats ont été dérivées les affinités protoniques et les basicités en phase gazeuse. [Traduit par la Rédaction]Mots-clés : dérivés protonés du cyclopropane et de la cyclopropanone, enthalpie, énergie de Gibbs, affinité protonique, basicité en phase gazeuse, théorie quantique des atomes dans les molécules.

A theoretical study of the strong interactions between carbon dioxide and OH+ and NH2 + products resulting from protonation of 1,2-dioxirane-3-one and 1,2-oxaziridine-3-one, respectively

“…In addition, the QTAIM topological parameters calculated at the bond critical point [electron charge density, q(r b ), Laplacian of electron charge density, r 2 q(r b ) and total electronic energy density, H(r b )] showed that the C3-O2 and C3-N2 bonds in these molecules are slightly stronger than the C-O single bond in formic acid and C-N single bond in N-methylacetamide, respectively. However, when the heteroatoms and N2 in (1) and (2) species, respectively, are ring protonated, the C3-O2 and C3-N2 bonds are broken and the O1-O2 and O1-N2 bonds are formed, despite the strength of the C3-O2 and C3-N2 bonds in the neutral molecules [30]. That is, non-ringprotonated derivatives of the (1) and (2) species are in fact complexes of carbon dioxide and the cations OH ?…”

The Reaction of CO2 with a Borylnitrene: Formation of an 3‐Oxaziridinone

“…We here report for the first time the reaction of a borylnitrene with CO 2 and show that this results in an 1,2‐oxaziridin‐3‐one derivative [50] . These are the smallest possible cyclic carbamates, which were suggested as reactive intermediates [51–57] and have been studied computationally before, [58–61] but never could be isolated.…”

“…[35,42] A particular reactive derivative is super electrophilic difluorovinylidene that inserts into methane and dihydrogen at 20-40 K. [43][44][45][46][47][48][49] We here report for the first time the reaction of a borylnitrene with CO 2 and show that this results in an 1,2oxaziridin-3-one derivative. [50] These are the smallest possible cyclic carbamates, which were suggested as reactive intermediates [51][52][53][54][55][56][57] and have been studied computationally before, [58][59][60][61] but never could be isolated.…”

The Reaction of CO2 with a Borylnitrene: Formation of an 3‐Oxaziridinone

“…[35,42] A particular reactive derivative is super electrophilic difluorovinylidene that inserts into methane and dihydrogen at 20-40 K. [43][44][45][46][47][48][49] We here report for the first time the reaction of a borylnitrene with CO 2 and show that this results in an 1,2oxaziridin-3-one derivative. [50] These are the smallest possible cyclic carbamates, which were suggested as reactive intermediates [51][52][53][54][55][56][57] and have been studied computationally before, [58][59][60][61] but never could be isolated.…”

“…We here report for the first time the reaction of a borylnitrene with CO 2 and show that this results in an 1,2‐oxaziridin‐3‐one derivative. [50] These are the smallest possible cyclic carbamates, which were suggested as reactive intermediates[ 51 , 52 , 53 , 54 , 55 , 56 , 57 ] and have been studied computationally before,[ 58 , 59 , 60 , 61 ] but never could be isolated.…”