Direct Evidence for Synchronicity between Rotation along Cα−C′ and Pyramidalization of C′ in Amides

Banerjee, S and Gupta, SK and Prabhakaran, EN (2023) Direct Evidence for Synchronicity between Rotation along Cα−C′ and Pyramidalization of C′ in Amides. In: ChemistrySelect, 8 (17).

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Abstract

In amides, the presence of sinusoidal synchronicity between rotational motion along Cα−C′ σ-bond (τ rotation) and the concomitant pyramidalization of C′ (θ) is evidenced for the first time in solution. Temperature-dependent 1H NMR and DFT simulations on suitable amide models (iBui−−Proi−Xaai+1−OMe; iBu is isobutyryl) reveal the perturbation in synchronicity when τ-rotation is ‘locked’ with interactions, resulting in a strain on the amide bond, which influences a decrease in energy barrier for the amide bond cis/trans isomerism by ∼1.68 kcal/mol.

Item Type:	Journal Article
Publication:	ChemistrySelect
Publisher:	John Wiley and Sons Inc
Additional Information:	The copyright for this article belongs to the John Wiley and Sons Inc.
Keywords:	cis/trans; Isomerism; Pyramidalization; Rotation; Synchronicity
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	15 Jun 2023 07:52
Last Modified:	15 Jun 2023 07:52
URI:	https://eprints.iisc.ac.in/id/eprint/81943

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