Theoretical characterization of the chemical bonds of some three-membered ring compounds through QTAIM theory

Abstract

In this paper, we investigate the nature of the carbonyl and the intraring C-C, C-N, C-O, N-N, O-O and N-O bonds of cyclopropanone and the following cyclopropanone derivatives: aziridine-2-one (1); oxirane-2-one (2); 1,2-diaziridine-3-one (3); 1,2-dioxirane-3-one (4); 1,2-oxaziridine-3-one (5); cyclopropane-1,2-dione (6); aziridine-2,3-dione (7); and oxirane-2,3-dione (8). The intramolecular distribution of the electronic charge density and the L(r) = -r 2 q(r) function have been investigated within the framework of the quantum theory of atoms in molecule theory. This methodology allowed us to characterize the bonds of cyclopropanone and the cyclopropanone derivatives studied here.

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

“…Recently, we have studied through the QTAIM, the nature of the bonds of the small-ring lactone and lactam 1,2-dioxirane-3-one and 1,2-oxaziridine-3-one (see Scheme 1 for the atom numbering) [29]. In that work, it was shown by QTAIM that there is not a bond critical point and bond path between the atoms O1 and O2, and O1 and N2, respectively.…”

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

“…This is in agreement with the atoms in molecules analysis that found no N-O bond critical point for the parent oxaziridinone. [58] We could not observe any indication for formation of this higher energy isomer of 5 or for ring opening to the more stable isocyanatoxy borane 8. The latter rearrangement is associated with a sizeable barrier (see Figure S8).…”

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.…”

“…1.446 Å). [ 58 , 64 ] The NBO analysis revealed that the NO natural bond orbital is comprised of natural atomic hybrids (NAH) on both nitrogen and oxygen atoms with p character of 96 % each. The high percentage of p and a low percentage of s (4 % on each NAHs) character of the NAH explains the unusually long NO bond in 5 .…”