| Full text | |
| Author(s): |
Batista, Patrick R.
[1]
;
Karas, Lucas J.
[2]
;
Viesser, Renan V.
[3]
;
de Oliveira, Cynthia C.
[4]
;
Goncalves, Marcos B.
[4]
;
Tormena, Claudio F.
[3]
;
Rittner, Roberto
[3]
;
Ducati, Lucas C.
[1]
;
de Oliveira, Paulo R.
[5]
Total Authors: 9
|
| Affiliation: | [1] Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, Av Prof Lineu Prestes, POB 748, BR-05508000 Sao Paulo, SP - Brazil
[2] Univ Houston, Dept Chem, Univ Pk, Houston, TX 77204 - USA
[3] Univ Estadual Campinas, Inst Chem, Phys Organ Chem Lab, POB 6154, BR-13083970 Campinas, SP - Brazil
[4] Fed Technol Univ Parana, Acad Dept Phys, BR-80230901 Curitiba, Parana - Brazil
[5] Fed Technol Univ Parana, Dept Chem & Biol, Conformat Anal & Renewable Resources Lab, POB 5000, BR-81280340 Curitiba, Parana - Brazil
Total Affiliations: 5
|
| Document type: | Journal article |
| Source: | Journal of Physical Chemistry A; v. 123, n. 40, p. 8583-8594, OCT 10 2019. |
| Web of Science Citations: | 0 |
| Abstract | |
This study expands the knowledge on the conformational preference of 1,3-amino alcohols in the gas phase and in solution. By employing Fourier transform infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, density functional theory (DFT) calculations, quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO) analysis, and molecular dynamics (MD), the compounds 3-aminopropan-1-ol (1), 3-methylaminopropan-1-ol (2), and 3-dimethylaminopropan-1-ol (3) are evaluated. The results show that the most stable conformation of each compound in the gas phase and in nonpolar solvents exhibited an O-H center dot center dot center dot N intramolecular hydrogen bond (IHB). Based on the experimental and theoretical OH-stretching frequencies, the IHB becomes stronger from 1 to 3. In addition, from the experimental NMR J-couplings, the IHB conformers are predominant in nonbasic solvents, representing 70-80% of the conformational equilibrium, while in basic solvents, such conformers only represent 10%. DFT calculations and QTAIM analysis in the gas phase support the occurrence of IHBs in these compounds. The MD simulation indicates that the non-hydrogen-bonded conformers are the lowest energy conformations in the solution because of molecular interactions with the solvent, while they are absent in the implicit solvation model based on density. NBO analysis suggests that methyl groups attached on the nitrogen atom affect the charge transfer energy involved in the IHB. This effect occurs mostly because of a decrease in the s-character of the LPN orbital along with weakening of the charge transfer from LPN to sigma{*}OH, which is caused by an increase in the C-C-N bond angle. (AU) | |
| FAPESP's process: | 17/20890-1 - Evaluation of shielding and transmission mechanisms of 1H, 13C and 19F NMR |
| Grantee: | Renan Vidal Viesser |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |
| FAPESP's process: | 17/17750-3 - Solvent Effect in NMR Parameters by ab initio Molecular Dynamics |
| Grantee: | Lucas Colucci Ducati |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 15/08541-6 - Nuclear magnetic resonance spectroscopy: beyond molecular structure assignment |
| Grantee: | Claudio Francisco Tormena |
| Support Opportunities: | Research Projects - Thematic Grants |
| FAPESP's process: | 14/25903-6 - Molecular structure of some amino acids and dipeptides |
| Grantee: | Roberto Rittner Neto |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 18/07308-4 - Effect of solvent on shielding tensor and coupling constant calculations of platinum (iii) dinuclear complexes via ab initio molecular dynamics |
| Grantee: | Patrick Rodrigues Batista |
| Support Opportunities: | Scholarships in Brazil - Doctorate |