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Article
Computational Rationalization for the Observed Ground-State Multiplicities of Fluorinated Acylnitrenes
The Journal of Organic Chemistry
  • Matthew P. Sherman, Iowa State University
  • William S. Jenks, Iowa State University
Document Type
Article
Publication Version
Published Version
Publication Date
9-8-2014
DOI
10.1021/jo500664e
Abstract

Computational methods are used to investigate the mechanism by which fluorination of acetylnitrene reduces the stabilization of the singlet configuration. ΔEST is made more positive (favoring the triplet state) by 1.9, 1.3, and 0.7 kcal/mol by the addition of the first, second, and third fluorine, respectively, at the CR-CC(2,3)/6-311(3df,2p)//B3LYP/6-31G(d,p) level of theory. Smaller effects observed with substitution of β-fluorines in propanoylnitrene derivatives and examination of molecular geometries and orbitals demonstrate that the effect is due to inductive electron withdrawal by the fluorines, rather than hyperconjugation.

Comments

Reprinted (adapted) with permission from The Journal of Organic Chemistry, 79(19); Doi: 10.1021/jo500664e. Copyright 2014 American Chemical Society.

Copyright Owner
American Chemical Society
Language
en
File Format
application/pdf
Citation Information
Matthew P. Sherman and William S. Jenks. "Computational Rationalization for the Observed Ground-State Multiplicities of Fluorinated Acylnitrenes" The Journal of Organic Chemistry Vol. 79 Iss. 19 (2014) p. 8977 - 8983
Available at: http://works.bepress.com/william_jenks/8/