Silva, Weslley G. D. P., Daudet, Gabrielle, Perez, Sem, Thorwirth, Sven 
ORCID: 0000-0001-8200-6710 and van Wijngaarden, Jennifer ORCID: 0000-0001-6073-1153
(2021).
Conformational preferences of diallylamine: A rotational spectroscopic and theoretical study.
J. Chem. Phys., 154 (16).
MELVILLE:
AMER INST PHYSICS.
ISSN 1089-7690
Abstract
The conformational space of diallylamine (DAA) was investigated using rotational spectroscopy from 7 to 19 GHz aided by quantum chemical calculations. Extensive conformational searches using density functional theory B3LYP-D3(BJ) and the ab initio MP2 method with the aug-cc-pVTZ basis set identified a total of 42 minima for DAA within similar to 22 kJ mol(-1). This reveals a strikingly rich conformational landscape for this secondary amine with two equivalent substituents. Experimentally, transitions belonging to four low energy conformers (I, II, III, and IV) were unequivocally assigned in the rotational spectrum, and their patterns were confirmed by the presence of the hyperfine structure owing to the N-14 quadrupolar nucleus. The relative intensities of the observed transitions suggest a conformational energy ordering of I < II < III < IV. Natural bond orbital and non-covalent interaction calculations reveal that the geometric preferences for the observed conformers are governed by an interplay of subtle attractive interactions (including hyperconjugation involving the lone pair at nitrogen) and repulsive effects.
| Item Type: | Journal Article | ||||||||||||||||||||||||
| Creators: |
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| URN: | urn:nbn:de:hbz:38-571982 | ||||||||||||||||||||||||
| DOI: | 10.1063/5.0048699 | ||||||||||||||||||||||||
| Journal or Publication Title: | J. Chem. Phys. | ||||||||||||||||||||||||
| Volume: | 154 | ||||||||||||||||||||||||
| Number: | 16 | ||||||||||||||||||||||||
| Date: | 2021 | ||||||||||||||||||||||||
| Publisher: | AMER INST PHYSICS | ||||||||||||||||||||||||
| Place of Publication: | MELVILLE | ||||||||||||||||||||||||
| ISSN: | 1089-7690 | ||||||||||||||||||||||||
| Language: | English | ||||||||||||||||||||||||
| Faculty: | Unspecified | ||||||||||||||||||||||||
| Divisions: | Unspecified | ||||||||||||||||||||||||
| Subjects: | no entry | ||||||||||||||||||||||||
| Uncontrolled Keywords: |
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| URI: | http://kups.ub.uni-koeln.de/id/eprint/57198 |
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