Steric effects of polar substituents evaluated in terms of energy by means of isodesmic reactions

Abstract

Steric effects of various polar and some charged groups were estimated on sterically crowded cyclopropanecis-1,2-bisderivatives 2 or 3, in which the variable substituent is in the proximity of a t-butyl group or of a methyl group. The steric energy was evaluated with reference to the pertinent mono derivatives, that is as reaction energy of an isodesmic reaction, in which the crowded compound is formally synthesized from simple derivatives. Energies were calculated within the framework of the density functional theory at level B3LYP/6-311+G(d,p)//B3LYP/6-311+G(d,p) for 11 dipolar and 5 charged substituents. Interaction of charged substituents is not only steric (destabilizing) but also inductive (stabilizing). The steric effects evaluated in this way differ distinctly from the standard steric constants derived purely from the van der Waals radii of the substituents.