Ab Initio Study of the Relative Energies and Properties of Fluoroborazines

Abstract

In the effort to compute molecular properties more accurately and at a lower cost in terms of computational time, density functional theory has emerged as an alternative to more expensive methods to include correlation corrections. In this paper the optimized geometries, harmonic frequencies, and electronic energies of ab initio calculations performed on borazine and the fluorinated derivatives of borazine at the B3LYP/6-31G** and MP2(FC)/6-31G** levels of theory are presented. We compare the results of the density functional method with second-order perturbation theory and, where possible, compare experimental observations with computed properties. A qualitative assessment of the aromaticity of borazine as a function of fluoro substitution is proposed. The calculations indicate, at both levels of theory, evidence for in-plane π bonding between fluorine and boron and fluorine and nitrogen in the fluorinated deriatives of borazine.

In silico studies toward the recognition of fluoride ion by substituted borazines

“…The B-fluorinated borazines are more stable than the corresponding N-fluorinated borazines in agreement with the earlier reports [42]. The B3LYP and MP2 calculated binding energies in the gas phase show that the fluorine substituted borazines bind the F − and Cl − ions more strongly with boron atoms than the NH hydrogens of the same molecule (Figs.…”

“…It has been shown that B3LYP method is consistent with experimental values for structural properties and vibrational frequencies of borazine and its fluoro-derivatives [42]. The minima of all the geometries were confirmed by the frequency analysis.…”

Novel cations of xenon trifluoroborazine complexes: Structures, reactivities, and natural bonding orbital analysis

“…It is proven that B3LYP is capable of prediction of structural properties and vibrational frequencies of borazine, and its fluoroderivatives in good agreement with the experimental values, comparable to the results of second-order perturbation theory (MP2) method [12]. We applied large aug-cc-PVTZ correlation-consistent basis set to H, B, N, and F atoms [27,28] and Def2-TZVP to xenon atom [29].…”

“…3) with a relative energy of 194.97 kcal/mol is energetically unfavorable isomer. Parker and Davis [12] …”

Structural and Molecular Orbital Properties of Some Boroxine Derivatives-A Theoretical Study

“…25 It has been proposed that replacing hydrogen atoms of boron in borazine with more electronegative substituents, for example fluorines, will draw more electrons from nitrogen to boron, thereby enhancing the aromaticity of the molecule. 26 Parker et al 27 calculated the aromaticity of a series of fluoro derivaties of borazine by carrying out vibrational analysis, and concluded that fluorination on boron increases molecular aromaticity, while fluorination on nitrogen decreases it.…”