MRMP2, CCSD(T), and DFT Calculations of the Isomerization Barriers for the Disrotatory and Conrotatory Isomerizations of 3-Aza-3-ium-dihydrobenzvalene, 3,4-Diaza-3-ium-dihydrobenzvalene, and 3,4-Diaza-diium-dihydrobenzvalene

The Journal of Physical Chemistry. a
Jeffrey D VealsSteven R Davis

Abstract

The isomerizations of 3-aza-3-ium-dihydrobenzvalene, 3,4-diaza-3-ium-dihydrobenzvalene, and 3,4-diaza-diium-dihydrobenzvalene to their respective cyclic-diene products were studied using electronic structure methods with a multiconfigurational wave function and several single reference methods. Transition states for both the allowed (conrotatory) and forbidden (disrotatory) pathways were located. The conrotatory pathways of each structure all proceed through a cyclic intermediate with a trans double bond in the ring: this trans double bond destroys the aromatic stabilization of the π electrons due to poor orbital overlap between the cis and trans π bonds. The 3,4-diaza-3-ium-dihydrobenzvalene structure has C1symmetry, and there are four separate allowed and forbidden pathways for this structure. The 3-aza-3-ium-dihydrobenzvalene structure is Cssymmetric, and there are two separate allowed and forbidden pathways for this structure. For 3,4-diaza-3,4-diium-dihydrobenzvalene, there was a single allowed and single forbidden pathway due to the C2vsymmetry. The separation of the barrier heights for all three molecules was studied, and we found the difference in activation barriers for the lowest allowed and lowest forbidden pathways ...Continue Reading

References

Jul 20, 2007·Chemistry : a European Journal·Paul W AyersPaul Geerlings
Jan 31, 2012·Accounts of Chemical Research·Paul GeerlingsFrank De Proft
Apr 1, 2008·Journal of Chemical Theory and Computation·F De ProftP Geerlings

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