Targeting the Rich Conformational Landscape of N ‐Allylmethylamine Using Rotational Spectroscopy and Quantum Mechanical Calculations
| Autor: | Tamanna Poonia, Jennifer van Wijngaarden, Weslley G. D. P. Silva |
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| Rok vydání: | 2020 |
| Předmět: |
Physics
Steric effects Quantitative Biology::Biomolecules 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Hyperconjugation 01 natural sciences Atomic and Molecular Physics and Optics 0104 chemical sciences symbols.namesake Fourier transform Chemical physics symbols Rotational spectroscopy Physical and Theoretical Chemistry 0210 nano-technology Hyperfine structure Conformational isomerism Quantum tunnelling Natural bond orbital |
| Zdroj: | ChemPhysChem. 21:2515-2522 |
| ISSN: | 1439-7641 1439-4235 |
| DOI: | 10.1002/cphc.202000757 |
| Popis: | The highly variable conformational landscape of N-allylmethylamine (AMA) was investigated using Fourier transform microwave spectroscopy aided by high-level theoretical calculations to understand the energy relationship governing the interconversion between nine stable conformers. Spectroscopically, transitions belonging to four low energy conformers were identified and their hyperfine patterns owing to the 14 N quadrupolar nucleus were unambiguously resolved. The rotational spectrum of the global minimum geometry, conformer I, shows an additional splitting associated with a tunneling motion through an energy barrier interconnecting its enantiomeric forms. A two-step tunneling trajectory is proposed by finding transition state structures corresponding to the allyl torsion and NH inversion. Natural bond orbital and non-covalent interaction analyses reveal that an interplay between steric and hyperconjugative effects rules the conformational preferences of AMA. |
| Databáze: | OpenAIRE |
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