Strong Pancake 2e/12c Bond in π-Stacking Phenalenyl Derivatives Avoiding Bond Conversion |
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| Authors: | Dr Rong-Lin Zhong Dr Feng-Wei Gao Dr Hong-Liang Xu Prof Zhong-Min Su |
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| Institution: | 1. Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, 130023 P. R. China;2. Institute of Functional Material Chemistry, National & Local United Engineering Laboratory for Power Batteries, Department of Chemistry, Northeast Normal University, Changchun, 130024 P. R. China
School of Chemistry & Environmental Engineering, Changchun University of Science and Technology, Changchun, 130012 P. R. China;3. Institute of Functional Material Chemistry, National & Local United Engineering Laboratory for Power Batteries, Department of Chemistry, Northeast Normal University, Changchun, 130024 P. R. China |
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| Abstract: | The nature of the 2e/12c bond and its conversion to a carbon-carbon single bond in phenalenyl dimers have prompted a great deal of interests recently. In this work, we theoretically investigated a series of π-stacking phenalenyl derivatives with 2e/12c bonding character by density functional theory (DFT) calculations to elucidate origin of this unusual bond conversion. Results show that bond-conversion of the phenalenyl dimer easily occurs at room-temperature both dynamically and thermodynamically. However, bond-conversion of hetero π-stacking adducts, in which the two center carbon atoms were substituted by boron and nitrogen atoms, respectively, is much more difficult, because the 2e/12c bond is stabilized by its charge transfer character. Consequently, the bond-conversion is an endothermic process, albeit with a low conversion barrier. Interestingly, Lewis acid-base interactions would be induced by substitution of the center nitrogen atom to phosphorus atom. The 2e/12c bond is further stabilized by 5.9 kcal mol−1 and its conversion is also thermodynamically unfavorable. |
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| Keywords: | charge transfer density functional calculations 2e/12c bond Lewis acid-base interactions phenalenyl |
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