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

• DOI: 10.1007/s00894-012-1637-3
• Publication Date: 2012-10-22T05:31:35Z
• Authors: Eleonora Echegaray; Carlos Cárdenas; Sandra Rabi; Nataly Rabi; Sungmin Lee; Farnaz Heidar Zadeh; Alejandro Toro-Labbe; James S. M. Anderson; Paul W. Ayers
• Keywords: Fukui function; Reactivity; HOMO/LUMO; Non-bonding orbital

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.