التفاصيل البيبلوغرافية
| العنوان: |
Electrostatics Explains the Reverse Lewis Acidity of BH 3 and Boron Trihalides: Infrared Intensities and a Relative Energy Gradient (REG) Analysis of IQA Energies |
| المؤلفون: |
Leonardo J. Duarte (4510849), Wagner E. Richter (4510852), Roy E. Bruns (2145862), Paul L. A. Popelier (11466731) |
| سنة النشر: |
2021 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Environmental Sciences not elsewhere classified, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, reverse lewis acidity, main factor behind, lewis acidity trend, interacting quantum atom, increasing halogen electronegativity, acidity trend exhibited, relative energy gradient, topological analysis suggests, cctdp analysis shows, attractive electrostatic energy, 3 , iqa energies indicates, b – x, pyramidal geometry observed, electrostatic energy, repulsive energy, iqa energies, b charges, pyramidal geometry, pyramidal geometries, two processes, reaction path, infrared intensities, highly dependent |
| الوصف: |
The reaction path for the formation of BX 3 –NH 3 (X = H, F, Cl, Br) complexes was divided into two processes: (i) rehybridization of the acid while adopting a pyramidal geometry, and (ii) the complex formation from the pyramidal geometries of the acid and base. The interacting quantum atom (IQA) method was used to investigate the Lewis acidity trend of these compounds. This topological analysis suggests that the boron–halogen bond exhibits a considerable degree of ionicity. A relative energy gradient (REG) analysis on IQA energies indicates that the acid–base complex formation is highly dependent on electrostatic energy. With increasing halogen electronegativity, a higher degree of ionicity of the B–X is observed, causing an increase in the absolute value of X and B charges. This increases not only the attractive electrostatic energy between the acid and base but also enhances the repulsive energy. The latter is the main factor behind the acidity trend exhibited by trihalides. Changes in geometry are relevant only for complexes where BH 3 acts as an acid, where lower steric hindrance facilitates the adoption of the pyramidal geometry observed in the complex. The CCTDP analysis shows that infrared intensities of BX 3 –NH 3 are determined mostly by the atomic charges and not by the charge transfer or polarization. The opposite is observed in covalent analogues. |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/Electrostatics_Explains_the_Reverse_Lewis_Acidity_of_BH_sub_3_sub_and_Boron_Trihalides_Infrared_Intensities_and_a_Relative_Energy_Gradient_REG_Analysis_of_IQA_Energies/16661048 |
| DOI: |
10.1021/acs.jpca.1c05766.s001 |
| الاتاحة: |
https://doi.org/10.1021/acs.jpca.1c05766.s001 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.44D28B92 |
| قاعدة البيانات: |
BASE |