RESUMO
In the current work, the chemical reactivity of some trivalent phosphorus derivatives R2PR' towards polyhaloalkanes CCl3POR ' '2 was studied by the quantum method DFT/B3LYP/6-311G(d,p). The introduction of substituents for the trivalent phosphorus derivative and polyhaloalkane allowed us to have more information on these reactions. On the one hand, the calculation of reactivity indices derived from the DFT/B3LYP/6-311G(d,p) method and the gapLUMO - HOMO show that trivalent organophosphorus derivatives behave as nucleophiles, while polyhaloalkanes act as electrophiles. On the other hand, the calculation of the activation barrier and the determination of the free enthalpy variation prove that the kinetic and thermodynamic products of these reactions result from the nucleophilic attack of the phosphorus atom on the chlorine halogen. All these theoretical predictions are in very good agreement with the experimental results.
RESUMO
In this work we used density functional theory (DFT) B3LYP/6-31G*(d) to study the stoichiometric reaction between the product (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6,4,0,0(1.3)]dodec-9-ene (referred to here as P1) and dibromocarbene. We have shown that P1 behaves as a nucleophile, while dibromocarbene behaves as an electrophile; that the chemical potential of dibromocarbene is superior to that of P1 in absolute terms; and that P1 reacts with an equivalent quantity of dibromocarbene to produce two products: (1S,3R,8R,9S,11R)-10,10-dibromo-2,2-dichloro-3,7,7,11-tetramethyltetracyclo[6,5,0,0(1.3),0(9.11)] tridecane (referred to here as P2) and (1S,3R,8R,9R,11S)-10,10-dibromo-2,2-dichloro-3,7,7,11-tetramethyltetracyclo[6,5,0,0(1.3),0(9.11)] tridecane (referred to here as P3). P2 and P3 are formed at the α and ß sides, respectively, of the C2 = C3 double bond of P1. This reaction is exothermic, stereoselective and chemospecific, and is controlled by charge transfer. Regioselectivity of the reaction was interpreted using the Lee-Yang-Parr functional.
