Ion-Pair S 2 Reaction of OH and CH Cl: Activation Strain Analyses of Counterion and Solvent Effects.

We have theoretically studied the non-identity S 2 reactions of M OH +CH Cl (M =Li , Na , K , and MgCl ; n=0, 1) in the gas phase and in THF solution at the OLYP/6-31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (S 2-b) and frontside (S 2-f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects.