Abstract
A recent computational analysis of the stabilizing intramolecular OH···O contact in 1,2-dialkyl-2,3-epoxycyclopentanol diastereomers has been extended to thiiriane, aziridine and phosphirane analogues. Density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2) and CCSD(T) coupled-cluster computations with simple methyl and ethyl substituents indicate that electronic energies of the cis isomers are lowered by roughly 3 to 4 kcal mol−1 when the OH group of these cyclopentanol systems forms an intramolecular contact with the O, S, N or P atom on the adjacent carbon. The results also suggest that S and P can participate in these stabilizing intramolecular interactions as effectively as O and N in constrained molecular environments. The stabilizing intramolecular OH···O, OH···S, OH···N and OH···P contacts also increase the covalent OH bond length and significantly decrease the OH stretching vibrational frequency in every system with shifts typically on the order of −41 cm−1
Recommended Citation
B. E. Smith et al., "Cis/Trans Energetics in Epoxide, Thiirane, Aziridine and Phosphirane Containing Cyclopentanols: Effects of Intramolecular Oh···o,s,n and P Contacts," Molecules, vol. 24, no. 14, article no. 2523, MDPI, Jan 2019.
The definitive version is available at https://doi.org/10.3390/molecules24142523
Department(s)
Chemistry
Publication Status
Open Access
Keywords and Phrases
Coupled-cluster theory; Density functional theory (DFT); Intramolecular hydrogen bonding; Semipinacol rearrangement; Vibrational frequencies
International Standard Serial Number (ISSN)
1420-3049
Document Type
Article - Journal
Document Version
Final Version
File Type
text
Language(s)
English
Rights
© 2024 The Authors, All rights reserved.
Creative Commons Licensing
This work is licensed under a Creative Commons Attribution 4.0 License.
Publication Date
01 Jan 2019
PubMed ID
31295845
Comments
National Science Foundation, Grant CHE-1338056