| Full text | |
| Author(s): |
Total Authors: 4
|
| Affiliation: | [1] Univ Estadual Campinas, Chem Inst, BR-13083861 Campinas, SP - Brazil
[2] Univ Tecnol Fed Parana, Dept Chem Engn, BR-84017220 Ponta Grossa, Parana - Brazil
[3] Univ Manchester, Dept Chem, Manchester M13 9PL, Lancs - England
[4] Manchester Inst Biotechnol MIB, Manchester M1 7DN, Lancs - England
Total Affiliations: 4
|
| Document type: | Journal article |
| Source: | Journal of Physical Chemistry A; v. 125, n. 39, p. 8615-8625, OCT 7 2021. |
| Web of Science Citations: | 0 |
| Abstract | |
The reaction path for the formation of BX3-NH3 (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 BH3 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 BX3-NH3 are determined mostly by the atomic charges and not by the charge transfer or polarization. The opposite is observed in covalent analogues. (AU) | |
| FAPESP's process: | 18/24844-7 - Using atomic polar tensors and QCT parameters to train a machine learning model and predict Hammett constants. |
| Grantee: | Leonardo José Duarte |
| Support Opportunities: | Scholarships abroad - Research Internship - Doctorate (Direct) |
| FAPESP's process: | 18/08861-9 - Application of the QTAIM / CCTDP model and machine learning for the forecast of chemical reactivities |
| Grantee: | Roy Edward Bruns |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 17/22741-3 - Using atomic multipoles and developing machine learning models to investigate transition states |
| Grantee: | Leonardo José Duarte |
| Support Opportunities: | Scholarships in Brazil - Doctorate (Direct) |