Stereoelectronic effect in reactions of phosphoester bond rupture
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The potential surface profile of the interaction of the anion (CH3O)2PO2− with the nucleophile CH3O− in the gas phase and in aqueous solution has been calculated by the AMl method. The energy of the transition state of the reaction in the gas phase is very much dependent on the position of the equatorial methoxy group; the change in the activation barrier amounts to 6 kcal/mole. The stereoelectronic effect is due to electrostatic interaction of the dipole moment of the equatorial substituent with the charge of the attacking or leaving group. An accounting for solvation gives a considerable decrease in the stereoelectronic effect.
KeywordsAqueous Solution Transition State Dipole Moment Electrostatic Interaction Methoxy
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