Modulations in restricted amide rotation by steric induced conformational trapping

Viswanathan V Krishnan, William B. Thompson, Joy J. Goto, Kalyani Maitra, Santanu Maitra

Research output: Contribution to journalArticle

10 Scopus citations

Abstract

The rotation around the amide bond in N,N-diethyl-m-toluamide (m-DEET) has been studied extensively and often used in laboratory instructions to demonstrate the phenomenon of chemical exchange. Herein, we show that a simple modification to N,N-diethyl-o-toluamide (o-DEET) significantly alters the dynamics of the restricted rotation around the amide bond due to steric interactions between the ring methyl group and the two N-ethyl groups. This alters the classic two-site exchange due to restricted rotation around the amide bond, to a three-site exchange, with the third conformation trapped at a higher-energy state compared to the other two. This often overlooked phenomenon is elucidated using variable-temperature NMR, two-dimensional exchange spectroscopy and molecular modeling studies.

Original languageEnglish (US)
Pages (from-to)124-127
Number of pages4
JournalChemical Physics Letters
Volume523
DOIs
StatePublished - Jan 27 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

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