Theoretical study of the electrophilic substitution reactivity in benzocyclobutadiene and biphenylene

Abstract

The electronic and geometric structures of benzocyclobutadiene ( 1), biphenylene ( 2) and their protonated forms are studied by the ab initio HF 6-31G * and MP2(fc)/6-31G * //HF/6-31G * methods. It is shown that β-protonated species are more stable in both cases indicating greater susceptibility of the β-positions towards electrophilic substitutions. This finding is rationalized by the lower π-electronic energy estimated by the valence bond resonance structures and a decreased antagonism between σ- and π-electrons in β-Wheland intermediates. The inherent generalized strain energies in the parent compounds ( 1) and ( 2) are estimated by homodesmic reactions. It is found that the intrinsic destabilization energy is ≈ 8 kcal mol −1 higher in 1, which is interpreted as the inability of the peripheral double bond to escape the cyclobutadiene antiboding pattern in an efficient way. The semiempirical AMI calculations give correct qualitative results, but fail at the quantitative level.