Understanding the local reactivity in polar organic reactions through electrophilic and nucleophilic Parr functions

Abstract

Building upon our recent studies devoted to the bonding changes in polar reactions [RSC Advances, 2012, 2, 1334 and Org. Biomol. Chem., 2012, 10, 3841], we propose herein two new electrophilic, P⁺_k, and nucleophilic, P⁻_k, Parr functions based on the spin density distribution at the radical anion and at the radical cation of a neutral molecule. These local functions allow for the characterisation of the most electrophilic and nucleophilic centres of molecules, and for the establishment of the regio- and chemoselectivity in polar reactions. The proposed Parr functions are compared with both, the Parr–Yang Fukui functions [J. Am. Chem. Soc. 1984, 106, 4049] based on frontier molecular orbitals, and Yang–Mortier condensed Fukui functions [J. Am. Chem. Soc. 1986, 108, 5708] based on Mulliken charges.