Control of the diatropic pi ring current in strained benzenes: effects of annelation with cyclopropa, cyclobuta, and cyclobutadieno clamping groups.
Direct visualization of the pi current density maps of highly strained annelated benzenes containing cyclopropa, cyclobuta, and cyclobutadieno clamps, alone and in combination, using a reliable distributed-origin, coupled Hartree-Fock method, shows the robustness of the classical benzene diatropic pi ring current. When only saturated clamps are used, the benzene ring current is essentially unchanged. In contrast, annelation with one or more cyclobutadieno clamps disrupts the benzene ring current. Analysis of orbital contributions to the current density maps gives a unified account of these observations in terms of the nature of the HOMO-LUMO transition.
Soncini
Alessandro
A
School of Chemistry, University of Exeter, Stocker Road, Exeter EX4 4QD, UK.
Havenith
Remco W A
RW
Fowler
Patrick W
PW
Jenneskens
Leonardus W
LW
Steiner
Erich
E