Theoretical study of the regioselectivity of the reaction between tetrachloromethane and trivalent phosphorus derivatives using the DFT B3LYP/6-31G(d) method

Abstract

In this study we used the DFT B3LYP/6-31G(d) method to determine certain thermodynamic properties, transition states, energies of the highest occupied and lowest unoccupied molecular orbits (HOMO and LUMO respectively), the difference between the two (eLUMO – eHOMO), global indices and chemical potentials of the reaction between tetrachloromethane and the following trivalent phosphorus derivatives: P(OEt)3, (NEt2)P(OEt)2 , (NEt2)2P(OEt) and (NEt2)3P. Our results show that the trivalent phosphorus derivatives behave as nucleophiles, while tetrachloromethane behaves as an electrophile. The nucleophilic attack takes place preferentially at the chlorine atom of the tetrachloromethane rather than at the carbon atom. The reaction is exothermic and regioselective, and the reaction mechanism is controlled by charge transfer. These results are comparable to those obtained experimentally.