Faculty and Student Publications
Document Type
Article
Publication Date
1-1-2019
Abstract
c 2019 by the authors 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
Relational Format
journal article
Recommended Citation
Smith, B. E., Carr, J. M., & Tschumper, G. S. (2019). Cis/Trans Energetics in Epoxide, Thiirane, Aziridine and Phosphirane Containing Cyclopentanols: Effects of Intramolecular OH⋯O, S, N and P Contacts. Molecules, 24(14), 2523. https://doi.org/10.3390/molecules24142523
DOI
10.3390/molecules24142523
Accessibility Status
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