Exceptionally Pyramidalized Olefins: A Theoretical Study of the Cyclopropenyl Fused Tricycles Tricyclo[3.2.1.02,4]oct-2(4)-ene, Tricyclo[3.2.1.02,4]octa-2(4),6-diene, Tricyclo[3.2.2.02,4]non-2(4)-ene, and Tricyclo[3.2.2.02,4]nona-2(4),6-diene
journal contributionposted on 29.12.1999, 00:00 authored by Richard Vaughan Williams, Michael E. Colvin, Ngoc Tran, Ronald N. Warrener, Davor Margetic
RHF, MP2, and TCSCF ab initio theory and B3LYP, B3PW91, and SVWN density functional theory were used to study the series of cyclopropenyl-fused tricycles 9−12. In each of 9−12, the cyclopropenyl double bond is exceptionally pyramidalized (butterfly angle ψ ∼41−50°) with both endo and exo bent isomers. In the norbornyl systems (9 and 10), the endo bent isomers are more stable than the exo bent isomers, whereas in the bicyclo[2.2.2]octadiene 12 the reverse is true with the exo bent isomer being the low energy form. The activation barriers for the endo/exo interconversions are calculated to be relatively low (ΔH⧧ ∼6−13 kcal/mol).