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

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 isomer...

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Bibliographic Details
Published in:Journal of organic chemistry 2000-01, Vol.65 (2), p.562-567
Main Authors: Williams, Richard Vaughan, Colvin, Michael E, Tran, Ngoc, Warrener, Ronald N, Margetic, Davor
Format: Article
Language:English
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Summary: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).
ISSN:0022-3263
1520-6904
DOI:10.1021/jo991496+