QUANTUM-CHEMICAL INVESTIGATION OF THE INITIATION ACTIVITY OF ALKYLXYLTHIUM AND ALKOXYLITHIUM COMPOUNDS COMPARED TO ACRYLONITRILE

Using the method of modified neglect of differential overlap, we calcu lated the formation heats of pre-reaction complexes, transition states , and activation energies of the reaction of addition of methoxide and lithium n-butoxide to acrylonitrile. Comparison of the calculated val ues of activation energy with those obtained earlier, for the reaction s of the addition of methyllithium and n-butyllithium to acrylonitrile shows that lithium alkyles are more reactive as initiators of acrylon itrile polymerization than lithium alkoxydes. As follows from the calc ulated values of the ionization potentials of initiators under study, this difference correlates with the difference in the electron-donatin g abilities of the compounds RLi and ROLi with respect to the same mon omer.