Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

9-8-2014

Journal or Book Title

The Journal of Organic Chemistry

Volume

79

Issue

19

First Page

8977

Last Page

8983

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

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