Computational Rationalization for the Observed Ground-State Multiplicities of Fluorinated AcylnitrenesThe Journal of Organic Chemistry
Publication VersionPublished Version
AbstractComputational 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.
Copyright OwnerAmerican Chemical Society
Citation InformationMatthew 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/