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In pursuit of negative Fukui functions: examples where the highest occupied molecular orbital fails to dominate the chemical reactivity

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Abstract

In our quest to explore molecules with chemically significant regions where the Fukui function is negative, we explored reactions where the frontier orbital that indicates the sites for electrophilic attack is not the highest occupied molecular orbital. The highest occupied molecular orbital (HOMO) controls the location of the regions where the Fukui function is negative, supporting the postulate that negative values of the Fukui function are associated with orbital relaxation effects and nodal surfaces of the frontier orbitals. Significant negative values for the condensed Fukui function, however, were not observed.

The −10−5isosurface of \( {f^{-}}\left( \mathbf{r} \right) \)(opaque silver surface) traces the nodal regions of the HOMO (translucent colored lobes, with different colors for different phases) of the phenoxide anion

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Acknowledgments

P.W.A. thanks the Canada Research Chairs and Natural Sciences and Engineering Research Council of Canada (NSERC) for funding. Computational facilities were provided by Sharcnet. E.E. and A.T.L. acknowledge financial support from Fondecyt through project N°1090460. C.C. acknowledge financial support from Fondecyt through project No 11090013 and also by Financiamiento basal para centros científicos y tecnológicos de excelencia. J.S.M.A. would like to thank NSERC and The Japan Society for the Promotion of Science (JSPS) for funding.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario, Canada

    Eleonora Echegaray, Carlos Cárdenas, Sandra Rabi, Nataly Rabi, Sungmin Lee, Farnaz Heidar Zadeh, James S. M. Anderson & Paul W. Ayers

  2. Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile

    Eleonora Echegaray & Alejandro Toro-Labbe

  3. Departamento de Física, Facultad de Ciencias, Universidad de Chile, 653, Santiago, Chile

    Carlos Cárdenas

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  1. Eleonora Echegaray
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Correspondence to Paul W. Ayers.

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Echegaray, E., Cárdenas, C., Rabi, S. et al. In pursuit of negative Fukui functions: examples where the highest occupied molecular orbital fails to dominate the chemical reactivity. J Mol Model 19, 2779–2783 (2013). https://doi.org/10.1007/s00894-012-1637-3

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  • DOI: https://doi.org/10.1007/s00894-012-1637-3

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