Abstract
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.
Highlights
Most polyhalomethanes such as tetrachloromethane CCl4 [1], chloroform CHCl3 [2,3], diethyl trichloromethyl phosphonate CCl3PO(OEt)2 [4,5] and trichloromethylphosphine oxide CCl3PO(Ph)2 [6] react with trialkylphosphites through the participation of a single halogen atom
The calculation of reactivity indices derived from the Density Functional Theory (DFT)/B3LYP/6-311G(d,p) method and the gapLUMO−Highest Occupied Molecular Orbital (HOMO) show that trivalent organophosphorus derivatives behave as nucleophiles, while polyhaloalkanes act as electrophiles
According to the results obtained, the most favored electrophilic-nucleophilic interaction is between the carbon atom of diethyltrichloromethyl phosphonate CCl3PO(OEt)2 and the chlorine halogen of trichloromethyl phosphine oxide CCl3PO(Ph)2 and the phosphorus atom which acts as nucleophilic site of trivalent phosphorus derivatives
Summary
Most polyhalomethanes such as tetrachloromethane CCl4 [1], chloroform CHCl3 [2,3], diethyl trichloromethyl phosphonate CCl3PO(OEt)2 [4,5] and trichloromethylphosphine oxide CCl3PO(Ph)2 [6] react with trialkylphosphites through the participation of a single halogen atom. It was concluded that the thermal reaction of triethylphosphite 1a with diethyltrichloromethyl phosphonate 2a takes place according to a nucleophilic attack of 1a on one of the chlorine atoms of 2a This has been verified at room temperature by reacting [9] the polyhaloalkane 2a with the more reactive phosphinite (Ph)2POCH3 than the phosphite (EtO)3P. We will perform a theoretical study using the DFT/B3LYP/6311G(d,p) method, of the reaction of CCl3POR′′2 with R2PR′ in order to specify its reaction mechanism
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