SYNTHESIS ON THE BASIS OF ELECTROGENERATED CARBENES .9. QUANTUM-CHEMICAL INVESTIGATION OF S(N)2 REACTIONS OF POLYHALOMETHANES AND THEIR ANIONS

A series of S(N)2 reactions with halomethanes as substrates and the co rresponding anions as nucleophiles were studied by the semiempirical M NDO and AM1 methods, taking into account solvent effects. Analysis of the kinetics, structures of reagents, intermediates and products, and charge distribution in them allows one to draw the conclusion that the retardation of S(N)2 reactions is stronger in solvents than in the ga s phase, and the rates of reactions involving anions with a lower numb er of halogen atoms are higher.