Fukui function propylene

FIGURE 18.1 (See color insert following page 302.) Propylene is susceptible to electrophilic attack on the double bond. This can be deduced by plotting (a) the Fukui function from below, / (r), or (b) the HOMO density, pHOMO(r), on the van der Waals surface of the molecule. 

In most cases, the orbital relaxation contribution is negligible and the Fukui function and the FMO reactivity indicators give the same results. For example, the Fukui functions and the FMO densities both predict that electrophilic attack on propylene occurs on the double bond (Figure 18.1) and that nucleophilic attack on BF3 occurs at the Boron center (Figure 18.2). The rare cases where orbital relaxation effects are nonnegligible are precisely the cases where the Fukui functions should be preferred over the FMO reactivity indicators [19-22], In short, while FMO theory is based on orbitals from an independent electron approximation like Hartree-Fock or Kohn-Sham, the Fukui function is based on the true many-electron density. 

The condensed Fukui functions for propylene and BF3 are given below. 

For propylene, the condensed Fukui function not only predicts that the electrophilic attack occurs on one of the doubly bonded carbon atoms, but it also predicts that there is a preference for the terminal carbon, in accordance with Markonikov s rule. Nucleophilic attack is predicted at the boron atom in BF3. 

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See also in sourсe #XX -- [ ]

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