Fulvalenes, Fulvenes, and Related Molecules: An ab Initio Study
journal contributionposted on 04.04.1997, 00:00 by Anthony P. Scott, Israel Agranat, P. Ulrich Biedermann, Noel V. Riggs, Leo Radom
Ab initio calculations using conventional (HF/6-31G* and MP2/6-31G*) and density functional theory (B-LYP/6-31G*) methods have been used to determine the structures of the [n]fulvene and [n,m]fulvalene (n, m = 3, 5, 7) series of molecules, with particular emphasis on heptafulvalene (n = m = 7: 12). Calculations have also been performed on the parent cycloalkenes: cyclopropene, cyclopentadiene, and cycloheptatriene (1−3, respectively). All the fulvenes (n = 3, 5, 7: 4−6, respectively) and the smaller fulvalenes (n = 3, m = 3, 5, 7: 7−9, respectively, and n = m = 5: 10) are found to be planar. Pentaheptafulvalene (n = 5, m = 7: 11) adopts a very slightly nonplanar Cs arrangement of the five- and seven-membered rings. Heptafulvalene (12) is predicted to have an anti-folded C2h structure, in accord with the X-ray crystal structure. We propose that the underlying reason for 11 and 12 adopting nonplanar conformations is the proximity of the H2 and H2‘ hydrogen atoms which promotes a distortion of the rings away from planarity at the central fulvalenic CC double bond. In the process, π-overlap is lost but this is partially regained by pyramidalization of the carbon centers in the seven-membered ring(s). The degree of folding is substantially more pronounced in 12 than in 11. Our calculated dipole moments, π-electron distributions, bond alternation parameters, and energy comparisons indicate that the unknown smallest fulvalene, triafulvalene (7), is highly destabilized with localized bonding while triapentafulvalene (8), which is also unknown, is predicted to be stabilized and quite delocalized, consistent with Hückel 4n + 2 considerations.