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T M S S: Heoretical Odeling of Emibullvalene Ynthesis
T M S S: Heoretical Odeling of Emibullvalene Ynthesis
CHEM260 FALL2016
KEYANG SUN
1. INTRODUCTION
All calculations were performed using QChem 4.4.1[8] using B3LYP/6-31G** level of
theory; all frequency calculations were computed at 298.15K. The fluxional thermal barrier to
the degenerate cope rearrangement of SBV is computed to be 4.35 kcal/mol (figure 1), which
agrees with the experimental value of 4.8±0.2 kcal/mol.[7]
Figure 1. Enthalpy (298.15K) diagram for the [3,3] sigmatropic rearrangement of SBV
Qualitatively, the facile nature of the pericyclic reaction can be attributed to the benzene-
like six-membered ring transition state (TS), which gives significant aromatic stabilization. The
six-electron reaction follows the Hückel topology in a disrotatory [π2S+σ2S+π2S] reaction. The
reactant and product SBV, which belong to the CS symmetry group, are connected through a TS
structure of C2V symmetry that contains elements of both CS groups; this conservation of
symmetry is consistent with principles of electrocyclization reaction. In the computed wave
function of the lowest unoccupied molecular orbital (LUMO) of SBV, it is possible to delineate
the overlaps visually (figure 2); the LUMO of the π systems in the reactant SBV shows a
constructive supraficial interaction between the LUMO of C3 and C4 (shown in red) to form the
σ-bond in the product SBV. The σ-bond (shown in red) in the reactant SBV mixes with the π
LUMO between C and C in a disrotatory fashion to form the π system between C1 and C2, and
C6 and C5 in the product SBV.
At the transition state, the highest occupied molecular orbital (HOMO) wave function
resembles one of the two degenerate HOMOs of the benzene π system from a simple Frost
diagram analysis (figure 3). The Cope rearrangement TS can also be viewed as constructive
mixing of the nonbonding LUMO of two allyl or propylene systems between C1, C2, C3 and C4,
C5, C6; this is evident in the calculated TS structure: the bond lengths between C1 and C2, C2
and C3, C4 and C5 and, C5 and C6 are all equivalent at 1.39Å.
The reaction of 1,2,4,5-tetrazine and 3,3’-bicyclopropenyl to SBV was modeled via the
mechanism shown in figure 5 to yield the minimum free energy path shown in figure 4
calculated at the B3LYP/6-31G** level of theory at 298.15K; The intermediates were optimized
individually, each accompanied by a frequency and a single point energy calculation, which
produced enthalpy, entropy values as well as the intrinsic electronic energy of the molecule. TS
were determined via the freezing string method to obtain intermediate structures along the
reaction coordinate for reaction steps 1,2, 3 and 4; a transition state search is performed after,
followed by a frequency and single point energy calculation.
Figure 4. Free-energy (298.15K) diagram of SBV synthesis. The elementary steps are labeled
according to the reaction mechanism shown in figure 5.
𝐫𝟏 = 𝐤 𝐓𝐒𝐓
𝐀𝐁 𝐭𝐞𝐭𝐫𝐚𝐳𝐢𝐧𝐞 [𝐛𝐢𝐜𝐲𝐜𝐥𝐨𝐩𝐫𝐨𝐩𝐞𝐧𝐲𝐥]
The rate constant can be calculated via transition state theory using the Eyring-Polanyi
equation, where 𝐤 𝐁 is the Boltzmann’s constant, T is the temperature, h is Planck’s constant, R
!
is the gas constant and 𝚫𝐆𝑨𝑩 is the free energy change from state A to state B as shown in Figure
4. From this, 𝐤 𝐓𝐒𝐓
𝐀𝐁 is found to be 1.42e-4 s-1.
!
𝐤𝐁𝐓 𝚫𝐆𝑨𝑩
𝐤 𝐓𝐒𝐓
𝐀𝐁 = 𝐞𝐱 𝐩 − = 𝟏. 𝟒𝟐×𝟏𝟎!𝟒 𝒔!𝟏
𝐡 𝐑𝐓
Some of the principle routes to SBV involves the isomerization of several cyclic
precursors (Figure 7): barrelene L, cyclooctatetraene K and tricyclo[3.3.0.02.8]octa-3,7-diene J.
Barrelene is most energetically similar to SBV within 1.4 kcal/mol, while compound J is higher
in energy by 28.2 kcal/mol and compound K is lower by 6.9 kcal/mol. In fact, it is shown by
Martin et. al. that cyclooctatetraene is the primary thermal decomposition product of SBV.[6]
Figure 7. Relative free-energies of various SBV precursors.
References:
[1] Semibullvalene. Chem 260 Suggested Project: Semibullvalene. https://docs.google.com/
document/u/1/d/1Tzlcdnr-dOqAOhSEHa7g9gKjTXAEfm6qreKOMEk9FYQ/pub (accessed Oct.
15, 2016)
[2] Sauer, J. et. al. “An one-pot synthesis of semibullvalenes and its mechanism.” Eur. J. Org.
Chem., 2002, 791-801.
[3] Zhang, S. et. al. ”Semibullvalene and Diazasemibullvalene: Recent Advances in the
Synthesis, Reaction Chemistry, and Synthetic Applications.” Acc. Chem. Res., 2015, 48 (7),
1823–1831.
[4] Computational Methods Summary. MCGF – College of Chemistry, University of California,
Berkeley. https://docs.google.com/document/u/1/d/1w68nqqqr-
OYZXv97yXHbA_xAfj2ZTMQY_bE5YRy5AZk/pub (accessed Oct. 15, 2016).
[5] Q-Chem 4.3 User’s Manual. http://www.q-chem.com/qchem-website/manual_4-1.html
(accessed Oct. 15, 2016).
[6] H. D. Martin, T. Urbanek, R. Walsh. “Thermal behavior of C8H8 hydrocarbons. 2.
Semibullvalene: kinetic and thermodynamic stability”. J. Am. Chem. Soc., 1985, 107 (19), pp
5532–5534.
[7] Cheng, A. K., et al. "Determination of the fluxional barrier in semibullvalene by proton and
carbon-13 nuclear magnetic resonance spectroscopy." Journal of the American Chemical
Society, 1974, 96 (9), pp2887-2891.
[8] Y. Shao, et. al. Advances in molecular quantum chemistry contained in the Q-Chem 4
program package.