On the Ability of Nitrogen to Serve as an Electron Acceptor in a Pnicogen Bond

Abstract

Whereas pnicogen atoms like P and As have been shown repeatedly to act as electron acceptors in pnicogen bonds, the same is not true of the more electronegative first-row N atom. Quantum calculations assess whether N can serve in this capacity in such bonds and under what conditions. There is a positive π-hole belt that surrounds the central N atom in the linear arrangement of NNNF, NNN-CN, and NNO, which can engage a NH3 base to form a pnicogen bond with binding energy between 3 and 5 kcal/mol. Within the context of a planar arrangement, the π-hole above the N in NO2OF, N­(CN)3, and CF3NO2 is also capable of forming a pnicogen bond, the strongest of which amounts to 11 kcal/mol with NMe3 as base. In their pyramidal geometry, NF3 and N­(NO2)3 engage with a base through the σ-hole on the central N, with variable binding energies between 2 and 9 kcal/mol. AIM and NBO provide somewhat different interpretations of the secondary interactions that occur in some of these complexes.

Screening of Oxygenated Aromatic Compounds for Potential Antifungal Activity against Geotrichum citri-aurantii through Structure–Activity Relationship Analysis

“…MESP mapping is an important tool to illustrate the charge distributions of a molecule in a 3D space and provide isosurface values with the location of negative and positive electrostatic potentials. , In the MESP mapping, the negative (red and yellow) and the positive (blue) regions correspond to nucleophilic and electrophilic centers, respectively . Differences in nucleophilicity and electrophilicity could affect the proton-donating or -accepting ability of the compounds, both of which, in turn, lead to the failure of molecules to interact with each other due to electrostatic repulsion .…”

“…31,32 In the MESP mapping, the negative (red and yellow) and the positive (blue) regions correspond to nucleophilic and electrophilic centers, respectively. 33 Differences in nucleophilicity and electrophilicity could affect the proton-donating or -accepting ability of the compounds, both of which, in turn, lead to the failure of molecules to interact with each other due to electrostatic repulsion. 34 The MESP maps (Figure 3) of the oxygenated aromatic compounds were generated.…”

Properties and Stabilities of Cyclic and Open Chains of Halogen Bonds

“…The latter are characterized by the replacement of the bridging proton by any of a wide assortment of other atoms, most more electronegative than H. These interactions are commonly categorized in reference to the family of elements from which this replacement bridging atom is drawn. The chalcogen bond, − for example, makes use of S, Se, and Te, while the involvement of P, As, or Sb leads to the designation as a pnicogen bond. − …”

Unique O═N...O Pnicogen Interactions in Nitromethane Dimers: Evidence Using Matrix Isolation Infrared Spectroscopy and Computational Methodology

“…Nitromethane, quite recently, has been found to be a prototypical molecule wherein its nitrogen atom, as an electron acceptor, could host pnicogen bonds. , The delocalization of nonbonding pair of electrons of nitrogen to form resonant π-bonds with the twin oxygen atoms is observed to generate a localized positive electrostatic potential (ESP) over nitrogen. This anisotropy in the ESP, a π-hole, is known to facilitate ON...X pnicogen bonds involving nitromethane as the Lewis acid due to nitrogen.…”